Hydrocarbon-conversion catalyst and its method of preparation

ABSTRACT

A new catalytic composition and its method of preparation are presented. The catalytic composition comprises a crystalline borosilicate and a porous refractory inorganic oxide, said borosilicate and said inorganic oxide having been intimately admixed with one another, said borosilicate comprising a molecular sieve material having the following composition in terms of mole ratios of oxides: 
     
         0.9±0.2 M.sub.2/n O:B.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O, 
    
     wherein M is at least one cation having a valence of n, Y is between 4 and about 600, and Z is between 0 and about 160. 
     The catalytic composition can be used for the conversion of hydrocarbon streams, e.g., the isomerization of xylene feedstocks.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part application of co-pendingapplication U.S. Ser. No. 897,360, filed in the United States Patent andTrademark Office on Apr. 18, 1978, said U.S. Ser. No. 897,360 being acontinuation-in-part application of applications, U.S. Ser. No. 733,267,filed in the United States Patent and Trademark Office on Oct. 18, 1976,and now abandoned; U.S. Ser. No. 819,974, filed on July 28, 1977, andnow abandoned; and U.S. Ser. No. 836,403, filed on Sept. 26, 1977, andnow abandoned. Each of these applications is incorporated by referenceherein and is made a part hereof, including but not limited to thoseportions of each which specifically appear hereinafter.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to novel crystalline borosilicates, catalystscontaining such borosilicates, and a method for preparing suchcatalysts. More particularly, this invention relates tohydrocarbon-conversion catalysts that contain the crystallineborosilicates, a method for preparing such catalysts, and varioushydrocarbon conversion processes using such crystalline borosilicates.Patent art that is relevant to such borosilicates can be found in U.S.Patent Classes 423-326, 252-458, and 260-668.

2. Description of the Prior Art

Zeolitic materials, both natural and synthetic, have been demonstratedin the past to have catalytic capabilities for many hydrocarbonprocesses. Zeolitic materials, often referred to as molecular sieves,are ordered porous crystalline aluminosilicates having a definitestructure with large and small cavities interconnected by channels. Thecavities and channels throughout the crystalline material are generallyuniform in size allowing selective separation of hydrocarbons.Consequently, these materials in many instances have come to beclassified in the art as molecular sieves and are utilized, in additionto the selective adsorptive processes, for certain catalytic properties.The catalytic properties of these materials are also affected, to someextent, by the size of the molecules which are allowed selectively topenetrate the crystal structure, presumably to be contacted with activecatalytic sites within the ordered structure of these materials.

Generally, the term "molecular sieve" includes a wide variety ofpositive-ion-containing crystalline materials of both natural andsynthetic varieties. They are generally characterized as crystallinealuminosilicates, although other crystalline materials are included inthe broad definition. The crystalline aluminosilicates are made up ofnetworks of tetrahedra of SiO₄ and AlO₄ moieties in which the siliconand aluminum atoms are cross-linked by the sharing of oxygen atoms. Theelectrovalence of the aluminum atom is balanced by the use of positiveions, for example, alkali-metal or alkaline-earth-metal cations.

Prior art developments have resulted in the formation of many syntheticcrystalline materials. Crystalline aluminosilicates are the mostprevalent and, as described in the patent literature and in thepublished journals, are designated by letters or other convenientsymbols. Exemplary of these materials are Zeolite A (Milton, in U.S.Pat. No. 2,882,243), Zeolite X (Milton, in U.S. Pat. No. 2,882,244),Zeolite Y (Breck, in U.S. Pat. No. 3,130,007), Zeolite ZSM-5 (Argauer,et al., in U.S. Pat. No. 3,702,886), Zeolite ZSM-11 (Chu, in U.S. Pat.No. 3,709,979), Zeolite ZSM-12 (Rosinski, et al., in U.S. Pat. No.3,832,449), and others.

Relevant art is the above U.S. Pat. No. 3,702,886, in which Argauer, etal., disclose the crystalline aluminosilicate Zeolite ZSM-5 and themethod for making the same. This patent teaches the production of azeolite wherein aluminum or gallium oxides are present in thecrystalline structure, along with silicon or germanium oxides. Aspecific ratio of the latter to the former is reacted to produce a classof zeolites designated ZSM-5, which is limited to crystalline alumino-or gallo-silicates or germanates and which has a specified X-raydiffraction pattern. The above ZSM-11 and ZSM-12 patents are similarlylimited to crystalline alumino- or gallo-silicates or germanates, alsohaving specified X-ray diffraction patterns.

As shown by Haag, et al., in U.S. Pat. No. 3,856,871, by Morrison, inU.S. Pat. No. 3,856,872, by Burress, in U.S. Pat. No. 3,856,873, and byHayward, in U.S. Pat. No. 3,856,874, such ZSM-type aluminosilicates areused suitably for the isomerization of xylenes.

Manufacture of the ZSM-type materials utilizes a mixed base system inwhich sodium aluminate and a silicon-containing material are mixedtogether with sodium hydroxide and an organic base, such astetrapropylammonium hydroxide or tetrapropylammonium bromide, underspecified reaction conditions, to form the desired crystallinealuminosilicate.

Dwyer, et al., in U.S. Pat. No. 3,941,871, claim and teach anorganosilicate having very little aluminum in its crystalline structureand possessing an X-ray diffraction pattern similar to the ZSM-5composition. This patent is considered relevant art.

Another relevant patent is U.S. Pat. No. 3,328,119, wherein Robsonconsiders a synthetic crystalline aluminosilicate containing a minoramount of boria as an integral part of its crystal framework. Thisreference has been cited by the Examiner during the prosecution of theabove-mentioned applications U.S. Ser. No. 819,974 and U.S. Ser. No.836,403.

Additional relevant art comprises U.S. Pat. Nos. 3,329,480; 3,329,481;4,029,716; and 4,078,009. Young, in U.S. Pat. Nos. 3,329,480 and3,329,481, discloses "zircono-silicates" and "titano-silicates",respectively. Kaeding, in U.S. Pat. Nos. 4,029,716 and 4,078,009,discloses a crystalline aluminosilicate zeolite having asilica-to-alumina ratio of at least about 12 and a constraint indexwithin the approximate range of 1 to 12, and having combined therewithboron in an amount of at least about 0.2 weight percent as a result ofreaction of the zeolite with a boron-containing compound.

Unland, et al., in U.S. Pat. Nos. 4,115,424 and 4,140,726 disclose animproved alkylation catalyst that comprises a crystallinealuminosilicate exemplified by a type X- or Y-zeolite, which catalystincludes potassium, rubidium, and/or cesium cations and contains boronand/or phosphorus. The aluminosilicates are modified to have thepotassium, rubidium, and/or cesium cations and the boron and/orphosphorus present. The boron or phosphorus components can beincorporated by inclusion in an ion exchange solution, or bysubsequently utilizing a solution of such component as a slurryingmedium for catalyst particles or as an impregnating medium to beabsorbed in the catalyst.

Plank, et al., in U.S. Pat. Nos. 3,140,249; 3,140,251; and 3,140,253,disclose the suspension of a molecular sieve material in a matrix of arefractory inorganic oxide and its distribution throughout said matrix.The preparation and use of cation-exchanged molecular sieves areconsidered.

The present invention is directed to catalysts that comprise crystallineborosilicates and that can be used for the conversion of hydrocarbonstreams, e.g., the isomerization of xylene feedstocks, and to thepreparation of such catalysts.

SUMMARY OF THE INVENTION

According to the present invention, there are provided a catalyticcomposition that is suitable for the conversion of hydrocarbon streams,its method of preparation, and hydrocarbon conversion processesemploying said catalytic composition. Broadly, the catalytic compositioncomprises a crystalline borosilicate and a porous refractory inorganicoxide, said borosilicate and said inorganic oxide having been intimatelyadmixed with one another, said borosilicate comprising a molecular sievematerial having the following composition in terms of mole ratios ofoxides:

    0.9±0.2 M.sub.2/n O:B.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O,

wherein M is at least one cation having a valence of n, Y is between 4and about 600, and Z is between 0 and about 160. The catalyticcomposition can comprise a catalytic support comprising a crystallineborosilicate suspended in and distributed throughout a matrix of arefractory inorganic oxide, such as alumina, said support having beenimpregnated with at least one catalytically-active metal, and can beprepared by a specified method of preparation. Broadly, the methodcomprises: (1) admixing a crystalline borosilicate in a finely-dividedstate with a refractory inorganic oxide to form a catalytic supportmaterial, said catalytic support material having said borosilicatesuspended in and distributed throughout the matrix of said inorganicoxide, said borosilicate comprising a molecular sieve material havingthe following composition in terms of mole ratios of oxides:

    0.9±0.2 M.sub.2/n O:B.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O,

wherein M is at least one cation, n is the valence of the cation, Y is avalue within the range of 4 to about 600, and Z is a value within therange of 0 to about 160; (2) impregnating said catalytic supportmaterial with a solution of a heat-decomposable compound of acatalytically-active metal to provide an impregnated material; (3)drying said impregnated material at a temperature of about 77° F. (25°C.) to about 392° F. (200° C.) for a period of about 10 minutes to about100 hours in air to obtain a dried impregnated material; and (4)calcining said dried impregnated material at a temperature within therange of about 752° F. (400° C.) to about 1,112° F. (600° C.) for aperiod of about 10 minutes to about 20 hours to provide said catalyticcomposition.

The catalytic support material can be prepared by either of thefollowing two techniques. It can be prepared, when the inorganic oxideis an alumina, by: (1) admixing said borosilicate in a finely-dividedstate with the alumina by mulling spray-dried alumina with 5 to 20 wt.%gamma-alumina hydrosol or beta-alumina trihydrate and with saidborosilicate to form a mixture that is suitable for extruding; (2)adding water in an amount that will yield an extrudate having about 20wt.% to about 50 wt.% water; (3) adding, if needed, an extrusion aid anda pore-diameter modifier; (4) extruding said resulting admixture to forman extruded admixture; (5) drying said extruded admixture in air at atemperature of about 77° F. (25° C.) to about 392° F. (200° C.) for aperiod of about 10 minutes to about 20 hours to obtain a driedextrudate; and (6) calcining said dried extrudate at a temperaturewithin the range of about 752° F. ( 400° C.) to about 1,112° F. (600°C.) for a period of about 10 minutes to about 20 hours to provide acalcined catalytic support material.

Moreover, it can be prepared also by: (1) admixing said borosilicate ina finely-divided state with a hydrosol, sol, or hydrogel of saidinorganic oxide in order to uniformly disperse said borosilicate in saidhydrosol, sol, or hydrogel of said inorganic oxide to form an admixture;(2) while continually stirring the admixture, adding a gelling medium topromote gellation and to form a gel; (3) drying said gel at atemperature within the range of about 77° F. (25° C.) to about 392° F.(200° C.) for a period of about 10 minutes to about 100 hours in thepresence of moving air to form a dried mixture; and (4) calcining saiddried mixture at a temperature within the range of about 752° F. (400°C.) to about 1,112° F. (600° C.) for a period of about 20 minutes toabout 20 hours to provide a calcined catalytic support material.

An alumina is a typical refractory inorganic oxide. Catalytically-activemetals include, but are not limited to, metals of Group VIB of thePeriodic Table of Elements, such as molybdenum, and metals of Group VIIIof the Periodic Table of Elements, such as nickel. Such metals may beincorporated into the catalytic composition by impregnation and/orcation-exchange techniques.

There is also provided a process for the conversion of a hydrocarbonstream, which process comprises contacting said stream at conversionconditions with a catalytic composition of the present invention. Inaddition, there is provided a process for the catalytic isomerization ofa zylene feed, which process comprises contacting said feed atisomerization conditions with a catalytic composition of the presentinvention.

DESCRIPTION AND PREFERRED EMBODIMENTS

The present invention relates to a catalytic composition employing anovel synthetic crystalline molecular sieve material, a crystallineborosilicate, a method for preparing said catalytic composition, and theuse of said catalytic composition for the conversion of hydrocarbonstreams.

The family of such crystalline borosilicate materials, which areidentified as AMS-1B borosilicates, has a particular X-ray diffractionpattern as is shown in the various tables hereinafter. Such crystallineborosilicate can generally be characterized, in terms of the mole ratiosof oxides, as follows in Equation I:

    0.9±0.2 M.sub.2/n O:B.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O, (I)

wherein M is at least one cation, n is the valence of the cation, Y isbetween 4 and about 600, and Z representing the water present in suchmaterial, is between 0 and about 160, or more.

In another instance, the claimed crystalline borosilcate can berepresented in terms of mole ratios of oxides for the crystallinematerial not yet activated or calcined at high temperatures, as followsin Equation II:

    0.9±0.2 [WR.sub.2 O+(1-W) M.sub.2/n O]:B.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O,                                              (II)

wherein R is an alkylammonium cation, M is at least one cation, n is thevalence of the cation, Y is a value between 4 and 600, Z is a valuebetween 0 and about 160, and W is a value greater than 0 and less than1.

In Equation I, M can represent an alkali-metal cation, analkaline-earth-metal cation, an ammonium cation, an alkylammoniumcation, a hydrogen cation, a catalytically-active-metal cation, ormixtures thereof. In Equation II, M can represent an alkali-metalcation, an alkaline-earth-metal cation, an ammonium cation, a hydrogencation, a catalytically-active-metal cation, or mixtures thereof.

Advantageously, the value for Y falls within the range of 4 to about500. Suitably, Y is 4 to about 300; preferably, about 50 to about 160;and more preferably, about 80 to about 120.

Suitably, Z is within the range of 0 to about 40.

The original cation "M" in the above formulations can be replaced inaccordance with techniques well known in the art, at least in part, byion exchange with other cations. Preferred replacing cations includetetraalkylammonium cations, metal ions, ammonium ions, hydrogen ions,and mixtures of the above. Particularly preferred cations are thosewhich render the AMS-1B crystalline borosilicate catalytically activeespecially for hydrocarbon conversion. These materials include hydrogen,rare earth metals, aluminum, metals of Groups IB, IIB and VIII of thePeriodic Table, noble metals, manganese, etc., and other catalyticallyactive materials and metals known to the art. The catalytically activecomponents can be present anywhere from about 0.05 to about 25 weightpercent of the AMS-1B crystalline borosilicate.

Members of the family of AMS-1B crystalline borosilicates possess aspecified and distinguishing crystalline structure. Two methods wereemployed to obtain X-ray diffraction patterns of various samples ofAMS-1B crystalline borosilicates.

In the first method, identified hereinafter as Method No. 1, a Phillipsinstrument which utilized copper K alpha radiation was employed. TheX-ray diffraction intensities versus two-theta were recorded on a stripchart using a proportional counter. The theta values recorded wereconverted to interplanar spacing values in Angstroms (A) using the Braggequation. The relative intensities (relative peak heights) werecalculated as (100 I/I_(o)), where I_(o) is the intensity of thestrongest recorded peak and I is the value actually read for theparticular interplanar spacing.

In the second method, identified hereinafter as Method No. 2, the X-raydiffractometer was a Phillips instrument which utilized copper K alpharadiation in conjunction with an AMR focusing monochromometer and atheta compensating slit, in which its aperture varies with the thetaangle. The output from the diffractometer was processed through aCanberra hardware/software package and reported by way of a strip chartand tabular printout. The compensating slit and the Canberra packagetend to increase the peak/background ratios while reducing the peakintensities at low theta angles [large interplanar spacings] andincreasing the peak intensities at high theta angles [small interplanarspacings.]

For ease of reporting the results obtained by either method, therelative intensities (relative peak heights) were arbitrarily assignedthe following values:

    ______________________________________                                        Relative Peak Height                                                                             Assigned Strength                                          ______________________________________                                        less than 10       VW (very weak)                                             10-19              W (weak)                                                   20-39              M (Medium)                                                 40-70              MS (medium strong)                                         greater than 70    VS (very strong)                                           ______________________________________                                    

These assigned strengths are used throughout this application.

An X-ray diffraction pattern obtained by means of Method No. 1 anddisplaying the significant lines in the indicated relative intensities(relative peak heights) and assigned strength for the AMS-1B crystallineborosilicates is presented in Table I hereinbelow:

                  TABLE I                                                         ______________________________________                                                          Relative     Assigned                                       Interplanar Spacings, d(A)                                                                      Intensity (I/I.sub.o)                                                                      Strength                                       ______________________________________                                        11.04 ± 0.2    100          VS                                             10.04 ± 0.2    68           MS                                             7.37 ± 0.15    2            VW                                             6.70 ± 0.1     7            VW                                             6.32 ± 0.1     10           W                                              5.98 ± 0.07    20           M                                              5.68 ± 0.07    10           W                                              5.53 ± 0.05    13           W                                              5.30 ± 0.05    3            VW                                             5.21 ± 0.05    3            VW                                             4.98 ± 0.05    9            VW                                             4.62 ± 0.05    3            VW                                             4.37 ± 0.05    5            VW                                             4.27 ± 0.05    10           W                                              4.07 ± 0.05    2            VW                                             4.00 ± 0.05    6            VW                                             3.83 ± 0.05    84           VS                                             3.72 ± 0.05    48           MS                                             3.64 ± 0.05    23           M                                              3.42 ± 0.05    9            VW                                             3.30 ± 0.05    11           W                                              3.23 ± 0.05    3            VW                                             3.16 ± 0.05    2            VW                                             3.12 ± 0.05    2            VW                                             3.04 ± 0.05    9            VW                                             2.98 ± 0.02    16           W                                              2.94 ± 0.02    10           W                                              2.86 ± 0.02    2            VW                                             2.83 ± 0.02    1            VW                                             2.73 ± 0.02    3            VW                                             2.59 ± 0.02    3            VW                                             2.55 ± 0.02    3            VW                                             2.51 ± 0.02    3            VW                                             2.48 ± 0.02    5            VW                                             2.45 ± 0.02    3            VW                                             2.39 ± 0.02    5            VW                                             2.00 ± 0.02    13           W                                              1.99 ± 0.02    14           W                                              1.94 ± 0.02    6            VW                                             1.91 ± 0.02    4            VW                                             1.86 ± 0.02    2            VW                                             1.81 ± 0.02    1            VW                                             1.75 ± 0.02    2            VW                                             1.66 ± 0.02    4            VW                                             1.56 ± 0.02    2            VW                                             ______________________________________                                    

When Method No. 1 is employed, the above X-ray pattern is characteristicof the AMS-1B crystalline borosilicate having the oxide mole formuladescribed in Equation I, which borosilicate has been calcined at 1,100°F. (593° C.) and wherein the tetraalkylammonium ion has been removedfrom the system by the calcination procedure.

In the following Table, the more significant interplanar spacings andtheir assigned strengths are summarized from Table I.

                  TABLE II                                                        ______________________________________                                        Interplanar Spacings, d(A)                                                                         Assigned Strength                                        ______________________________________                                        11.04 ± 0.2       VS                                                       10.04 ± 0.2       MS                                                       5.98 ± 0.07       M                                                        3.83 ± 0.05       VS                                                       3.72 ± 0.05       MS                                                       3.64 ± 0.05       M                                                        ______________________________________                                    

In instances in which the AMS-1B crystalline borosilicate in anas-produced state (prior to high temperature calcination, but after somereasonable amount of drying has taken place), is analyzed by X-raydiffraction analysis by Method No. 1, the crystalline borosilicategenerally is characterized by Equation II above and has an X-raydiffraction pattern showing the following significant lines:

                  TABLE III                                                       ______________________________________                                        Interplanar Spacing, d(A)                                                                          Assigned Strength                                        ______________________________________                                        11.04 ± 0.2       MS                                                       9.82 ± 0.2        MS                                                       9.60 ± 0.2        MW                                                       8.84 ± 0.2        VW                                                       7.37 ± 0.2        W                                                        7.02 ± 0.15       VW                                                       6.60 ± 0.1        VW                                                       6.32 ± 0.1        W                                                        5.90 ± 0.07       W                                                        5.68 ± 0.07       W                                                        5.53 ± 0.05       W                                                        5.27 ± 0.05       VW                                                       5.09 ± 0.05       VW                                                       4.95 ± 0.05       W                                                        4.57 ± 0.05       W                                                        4.44 ± 0.05       VW                                                       4.35 ± 0.05       W                                                        4.23 ± 0.05       W                                                        4.04 ± 0.05       VW                                                       3.97 ± 0.05       W                                                        3.80 ± 0.05       VS                                                       3.72 ± 0.05       M                                                        3.67 ± 0.05       MS                                                       3.60 ± 0.05       MS                                                       3.45 ± 0.05       VW                                                       3.41 ± 0.05       W                                                        3.30 ± 0.05       W                                                        3.28 ± 0.05       W                                                        3.23 ± 0.05       VW                                                       3.16 ± 0.05       VW                                                       3.12 ± 0.05       VW                                                       3.06 ± 0.05       W                                                        2.96 ± 0.02       W                                                        2.94 ± 0.02       W                                                        2.85 ± 0.02       VW                                                       2.76 ± 0.02       VW                                                       2.71 ± 0.02       W                                                        2.59 ± 0.02       W                                                        2.56 ± 0.02       VW                                                       2.49 ± 0.02       VW                                                       2.47 ± 0.02       W                                                        2.40 ± 0.02       VW                                                       2.38 ± 0.02       W                                                        2.33 ± 0.02       VW                                                       2.31 ± 0.02       VW                                                       2.28 ± 0.02       VW                                                       2.21 ± 0.02       VW                                                       2.19 ± 0.02       VW                                                       2.16 ± 0.02       VW                                                       2.10 ± 0.02       VW                                                       2.06 ± 0.02       VW                                                       2.00 ± 0.02       W                                                        1.99 ± 0.02       W                                                        1.94 ± 0.02       W                                                        1.90 ± 0.02       W                                                        1.86 ± 0.02       W                                                        1.82 ± 0.02       VW                                                       1.75 ± 0.02       W                                                        1.71 ± 0.02       VW                                                       1.66 ± 0.02       W                                                        ______________________________________                                    

In the following Table, the more significant interplanar spacings andtheir assigned strengths are summarized from Table III.

                  TABLE IV                                                        ______________________________________                                        Interplanar Spacing, d(A)                                                                          Assigned Strength                                        ______________________________________                                        11.04 ± 0.2       MS                                                       9.82 ± 0.2        MS                                                       3.80 ± 0.05       VS                                                       3.72 ± 0.05       M                                                        3.67 ± 0.05       MS                                                       3.60 ± 0.05       MS                                                       ______________________________________                                    

A typical X-ray diffraction pattern obtained by means of Method No. 2and displaying the significant lines which have relative intensities(relative peak heights) of 11 or higher for an AMS-1B crystallineborosilicate after calcination at 1,000° F. (538° C.) is shown in TableV hereinbelow.

                  TABLE V                                                         ______________________________________                                         Interplanar Spacing,                                                                           Relative    Assigned                                        d(A)              Intensity   Strength                                        ______________________________________                                        11.3 ± 0.2     38          M                                               10.1 ± 0.2     30          M                                               6.01 ± 0.07    14          W                                               4.35 ± 0.05    11          W                                               4.26 ± 0.05    14          W                                               3.84 ± 0.05    100         VS                                              3.72 ± 0.05    52          MS                                              3.65 ± 0.05    31          M                                               3.44 ± 0.05    14          W                                               3.33 ± 0.05    16          W                                               3.04 ± 0.05    16          W                                               2.97 ± 0.02    22          M                                               2.48 ± 0.02    11          W                                               1.99 ± 0.02    20          M                                               1.66 ± 0.02    12          W                                               ______________________________________                                    

An AMS-1B borosilicate which has been only subjected to mild drying at165° C. (as produced material) possesses an X-ray diffraction patternobtained by Method No. 2, which pattern has the following significantlines:

                  TABLE VI                                                        ______________________________________                                        Interplanar Spacing,                                                                            Relative    Assigned                                        d(A)              Intensity   Strength                                        ______________________________________                                        11.4 ± 0.2     19          W                                               10.1 ± 0.2     17          W                                               3.84 ± 0.05    100         VS                                              3.73 ± 0.05    43          MS                                              3.66 ± 0.05    26          M                                               3.45 ± 0.05    11          W                                               3.32 ± 0.05    13          W                                               3.05 ± 0.05    12          W                                               2.98 ± 0.02    16          W                                               1.99 ± 0.02    10          W                                               1.66 ± 0.02    20          M                                               ______________________________________                                    

As discussed in Example XII of the parent application, United StatesSer. No. 897,360, the X-ray diffraction patterns of crystalline AMS-1Bborosilicates can be represented in general terms by the informationshown in the following Table VII:

                  TABLE VII                                                       ______________________________________                                        X-ray Diffraction Pattern of AMS-1B Borosilicates                                        Assigned Strengths For                                             Interplanar              Calcined at                                          Spacings     All         1,000°  F.-1,100° F.                   ______________________________________                                        11.2 ± 0.2                                                                              W - VS      M - VS                                               10.0 ± 0.2                                                                              W - MS      M - MS                                               5.97 ± 0.07                                                                             W - M       W - M                                                3.82 ± 0.05                                                                             VS          VS                                                   3.70 ± 0.05                                                                             MS          MS                                                   3.62 ± 0.05                                                                             M - MS      MS                                                   2.97 ± 0.02                                                                             W - M       W - M                                                1.99 ± 0.02                                                                             VW - M      VW - M                                               ______________________________________                                    

Therefore, in broad terms, the X-ray diffraction patterns of crystallineAMS-1B borosilicates comprise the interplanar spacings shown in TableVII and the assigned strengths shown therein depending upon the presenceor absence of calcination of the material prior to X-ray diffractionanalysis.

The AMS-1B crystalline borosilicates of the present invention are usefulas catalysts for various hydrocarbon conversion processes and they aresuitable for chemical adsorption. Some of the hydrocarbon conversionprocesses for which the borosilicates appear to have relatively usefulcatalytic properties are fluidized catalytic cracking; hydrocracking;the isomerization of normal paraffins and naphthenes; the reforming ofnaphthas and gasoline-boiling-range feedstocks; the isomerization ofaromatics, especially the isomerization of alkylaromatics, such asxylenes; the disproportionation of aromatics, such as toluene, to formmixtures of other more valuable products including benzene, xylene, andother higher methyl substituted benzenes; hydrotreating; alkylation;hydrodealkylation; hydrodesulfurization; and hydrodenitrogenation. Theyare particularly suitable for the isomerization of alkylaromatics, suchas xylenes, and for the conversion of ethylbenzene. The AMS-1Bborosilicates, in certain ion-exchanged forms, can be used to convertalcohols, such as methanol, to useful products, such as aromatics orolefins.

When the AMS-1B crystalline borosilicate is used as a hydrocrackingcatalyst, hydrocracking charge stocks can pass over the catalyst attemperatures anywhere from about 500° F. (260° C.) to about 850° F.(454° C.) or higher using known molar ratios of hydrocarbon to hydrogenand varying pressures anywhere from a few up to many thousands of poundsper square inch, or higher. The weight hourly space velocity and otherprocess parameters can be varied consistent with the well-knownteachings of the art.

The specified AMS-1B crystalline borosilicate is also suitable as areforming catalyst to be used with the appropriate hydrogenationcomponents at well-known reforming conditions including temperatures ofanywhere from about 500° F. (260° C.) to about 1,050° F. (566° C.), ormore, pressures anywhere from a few up to 300 psig (2,172 KPa) to 1,000psig (6,998 KPa), and weight hourly space velocities andhydrogen-to-hydrocarbon mole ratios consistent with those well known inthe reforming art.

The present crystalline borosilicate is also suitable for hydrocarbonisomerization and disproportionation. It is especially useful for liquidor vapor phase isomerization of xylenes and especially the isomerizationof mixed xylenes to predominantly paraxylene products. Operatingconditions for the isomerization of a xylene feed broadly comprise atemperature of about 200° F. (93° C.) to about 1,000° F. (538° C.), ahydrogen-to-hydrocarbon mole ratio of about 0 to about 20, a weighthourly space velocity (WHSV) of about 0.01 weight unit of feed per hourper weight unit of catalyst (hr⁻¹) to about 90 hr⁻¹, and a pressure ofabout 0 psig (101 KPa) to about 1,000 psig (6,998 KPa). Advantageously,the conditions comprise a temperature of about 400° F. (204° C.) toabout 900° F. (482° C.), a hydrogen-to-hydrocarbon mole ratio of about 1to about 12, a WHSV of about 1 hr⁻¹ to about 20 hr⁻¹, and a pressure ofabout 10 psig (170 KPa) to about 500 psig (3,551 KPa). The preferredconditions for the isomerization of xylenes comprise a temperature ofabout 600° F. (316° C.) to about 850° F. (454° C.), ahydrogen-to-hydrocarbon mole ratio of about 2 to about 8, a WHSV ofabout 1 hr⁻¹ to about 10 hr⁻¹, and a pressure of about 100 psig (793KPa) to about 300 psig (2,172 KPa).

The choice of catalytically active metals to be placed on the AMS-1Bcrystalline borosilicate can be selected from any of those well known inthe art. Nickel seems to be especially appropriate for isomerization ofaromatics. When used as a catalyst in isomerization processes withsuitable cations placed on the ion-exchangeable sites within the AMS-1Bcrystalline borosilicate, reasonably high selectivities for productionof desired isomers are obtained.

The claimed AMS-1B crystalline borosilicates can also be used asadsorbents to selectively adsorb specific isomers or hydrocarbons ingeneral from a liquid or vapor stream, such as alcohols from water.

The ability for these materials to be stable under high temperatures orin the presence of other normal deactivating agents appears to make thisclass of crystalline materials relatively valuable for high-temperatureoperations including the cyclical types of fluidized catalytic crackingor other processing.

The AMS-1B crystalline borosilicates can be used as catalysts or asadsorbents whether in the alkali-metal or alkaline-earth-metal forms,the ammonium form, the hydrogen form, or any other univalent ormultivalent cationic form. Mixtures of cations may be employed. TheAMS-1B crystalline borosilicates can also be used in intimatecombination with a hydrogenating component, such as tungsten, vanadium,molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noblemetal, such as platinum or palladium, or rare earth metals, where ahydrogenation-dehydrogenation function is to be performed. Suchcomponents can be exchanged into the composition at the cationic sites,represented by the term "M" in the above formulae, impregnated therein,or physically intimately admixed therewith. In one example, platinum canbe placed on the borosilicate with a platinum-metal-containing ion.

The impregnation of a hydrogenation metal on the borosilicate or on asupport comprising the crystalline borosilicate suspended in anddistributed throughout a matrix of a porous refractory inorganic oxide,such as an alumina, often results in a suitable catalytic composition.For example, a catalyst comprising molybdenum impregnated on acomposition of AMS-1B crystalline borosilicate suspended in an aluminamatrix, when used to isomerize a feed of mixed xylenes, furnishes betterselectivity and higher by-product values.

The original cation associated with the AMS-1B crystalline borosilicatecan be replaced, as mentioned above, by a wide variety of other cationsaccording to techniques which are known in the art. Ion exchangetechniques known in the art are disclosed in many patents, includingU.S. Pat. No. 3,140,249, U.S. Pat. No. 3,140,251, and U.S. Pat. No.3,140,253, the teachings of which are incorporated by reference intothis specification.

A catalytically active material can be placed onto the borosilicatestructure by ion exchange, impregnation, or other suitable contactmeans, followed by washing, drying at about 150° F. (66° C.) to about600° F. (316° C.), and then calcining in a suitable atmosphere, such asair, nitrogen, other gases, or combinations thereof, at about 500° F.(260° C.) to about 1,500° F. (816° C.), typically about 1,000° F. (538°C.), usually for about 0.5 hour to about 20 hours. This procedure can berepeated one or more times. Advantageously, before placing acatalytically active metal ion on the borosilicate structure, theborosilicate is in the hydrogen form which, typically, is produced byexchange with ammonium ion followed by calcination.

Ion-exchange within the cationic site within the crystalline materialwill generally have a relatively insignificant effect on the overallX-ray diffraction pattern that the crystalline borosilicate materialgenerates. Small variations may occur at various spacings on the X-raypattern, but the overall pattern remains essentially the same. Smallchanges in the X-ray diffraction patterns can also be the result ofprocessing differences during manufacture of the borosilicate; however,the material will still fall within the generic class of AMS-1Bcrystalline borosilicates defined in terms of their X-ray diffractionpatterns as shown in the tables found herein, or in the examples thatfollow.

The crystalline borosilicate of the present invention can beincorporated as a pure borosilicate in a catalyst or adsorbent or can beadmixed with various binders or bases depending upon the intendedprocess use. In many instances, the crystalline borosilicate can bepelletized or extruded. The crystalline borosilicate can be combinedwith active or inactive materials, synthetic or naturally-occurringzeolites, as well as inorganic or organic materials which would beuseful for binding the borosilicate. Other well-known materials includemixtures of silica, silica-alumina, alumina sols, clays, such asbentonite or kaolin, or other binders well known in the art. Thecrystalline borosilicate can also be mixed intimately with porous matrixmaterials, such as silica-zirconia, silica-magnesia, silica-alumina,silica-thoria, silica-beryllia, silica-titania, as well as threecomponent compositions including, but not limited to,silica-alumina-thoria and many other materials well known in the art.The crystalline borosilicate content can vary anywhere from a few up to100 wt.% of the total finished product. Typical catalytic compositionscontain about 5 wt.% to about 80 wt.% borosilicate material.

The AMS-1B crystalline borosilicate generally can be prepared by mixingan aqueous medium of oxides of boron, an alkali metal or an alkalineearth metal, such as sodium, and silicon, together with alkylammoniumcations or a precursor of alkylammonium cations, such as an alkylamine,an alkylamine plus an alkyl hydroxide, an alkylamine plus an alkylhalide, or an alkylamine plus an alkyl acetate. The alkyl groups in thealkylammonium cations may be the same, or mixed, such as tetraethyl-, ordiethyl-dipropyl-ammonium cations. The mole ratios of the variousreactants can be varied considerably to produce the AMS-1B crystallineborosilicates. In particular, the mole ratios of the initial reactantconcentrations for producing the borosilicate can vary as is indicatedin Table VIII below.

Examples of oxides of boron are H₃ BO₃, B₂ O₃, and B₄ O₇. Examples ofoxides of silicon are silicic acid, sodium silicate, tetraalkylsilicates, and Ludox, which is a stabilized polymer of silicic acidmanufactured by E. I. du Pont de Nemours & Co. Suitable compounds of thealkali metals or alkaline earth metals are their hydroxides.

                  TABLE VIII                                                      ______________________________________                                                                       Most                                                          Broad  Preferred                                                                              Preferred                                      ______________________________________                                        SiO.sub.2 /B.sub.2 O.sub.3                                                                     5-400    10-150   10-80                                      R.sub.2 O+/(R.sub.2 O+ + M.sub.2/n O)                                                          0.1-1    0.2-0.97 0.3-0.97                                   OH.sup.- /SiO.sub.2                                                                            0.01-11  0.1-2    0.1-1                                      H.sub.2 O/OH.sup.-                                                                             10-4,000 10-500   10-500                                     ______________________________________                                    

where R is an alkylamine or alkylammonium cation, preferablytetra-n-propyl ammonium cation or tetraethyl ammonium cation, and M isat least one cation having the valence of n, such as an alkali-metal oran alkaline-earth-metal cation. The above quantities can be varied inconcentration in the aqueous medium.

During preparation, acidic conditions generally should be avoided. Whenammonium hydroxide is used as a base, borosilicates can be produced withinitial pH's of 5.8, or lower. When alkali metal hydroxides are used,the values of the ratio of OH⁻ /SiO₂ in Table VIII should furnish a pHof the system that broadly falls within the range of about 9 to about13.5. Advantageously, the pH of the reaction system falls within therange of about 10.5 to about 11.5. Preferably, the pH of the system isabout 10.8 to about 11.2. A proper pH is conducive to the incorporationof boron into the molecular sieve structure.

By simple regulation of the quantity of boron (represented as B₂ O₃) inthe reaction mixture, it is possible to vary the SiO₂ /B₂ O₃ molar ratioin the final product in a range of from about 40 to about 600, or more.In instances where an effort is made to minimize aluminum in theborosilicate crystal structure, the molar ratios of SiO₂ /Al₂ O₃ caneasily exceed a ratio of 2,000:1 to 3,000:1 or more. This ratio isgenerally only limited by the availability of aluminum-free rawmaterials.

Molar ratios of SiO₂ /B₂ O₃ in the final crystalline product can varyfrom 4 to about 600, or more. Actual laboratory preparations under thegeneral conditions described herein produce SiO₂ /B₂ O₃ molar ratiosstarting around 60 or lower. Lower ratios might be produced usingproduction methods which still are in the scope of the teachings of thisspecification.

Unit cell measurements of the AMS-1B crystalline borosilicates showed alinear decrease of the unit cell size with respect to an increasingboron concentration in the molecular sieve over a SiO₂ /B₂ O₃ range ofabout 80 to about 600. Ion-exchange in the AMS-1B borosilicate has shownalso that there is one equivalent of alkali metal or alkaline earthmetal per mole of boron, as required for electrovalent neutrality.

Under reasonably controlled conditions using the above information theclaimed AMS-1B crystalline borosilicate will be produced. Typicalreaction conditions include heating the reactants to a temperature ofanywhere from about 77° F. (25° C.) to about 572° F. (300° C.), orhigher, for a period of time of anywhere from about one hour to fourweeks, or more. Preferred temperature ranges are anywhere from about194° F. (90° C.) to about 482° F. (250° C.) with an amount of timenecessary for the precipitation of the AMS-1B crystalline borosilicate.A preferred reaction time varies from about 4 hours to about 2 weeks. Amore preferred temperature varies from about 212° F. (100° C.) to about482° F. (250° C.) and a more preferred reaction time varies from about 6hours to about 1 week. Especially preferred conditions include atemperature around 329° F. (165° C.) for a period of about 5 days.

The material thus formed can be separated and recovered by well-knownmeans, such as filtration. This material can be mildly dried foranywhere from a few hours to a few days at varying temperatures to forma dry cake which itself can then be crushed to a powder or to smallparticles and extruded, pelletized, or made into forms suitable for itsintended use. Typically, the material prepared after the mild dryingconditions will contain the alkylammonium ion within the solid mass anda subsequent activation or calcination procedure is necessary, if it isdesired to remove this material from the formed product.

Typically, the high temperature calcination conditions will take placeat temperatures anywhere from about 500° F. (260° C.) to about 1,600° F.(871° C.), or higher. Extreme calcination temperatures may provedetrimental to the crystal structure or may totally destroy it. There isgenerally no need for going beyond about 1,100° F. (593° C.) in order toremove the alkylammonium cation from the original crystalline materialformed.

In a typical preparation of an AMS-1B crystalline borosilicate, acompound of an alkali metal or an alkaline earth metal, such as sodiumhydroxide, and a compound of boron, such as boric acid, are dissolved inwater (preferably, distilled or deionized water). A tetraalkylammoniumcompound, such as tetra-n-propylammonium bromide, is added to the abovesolution and the pH of the resulting solution is adjusted to a value ofabout 11.0±0.2 by the addition of base or acid. A compound of silicon,such as silicasol, is added rapidly to the solution, while the solutionis being agitated vigorously. Vigorous agitation is continued for about15 minutes. After the pH of the resulting solution is adjusted to about11.0±0.2, it is placed in an autoclave that is maintained at atemperature of about 329° F. (165° C.). Preferably, a stirred autoclaveis used. The solution is kept in the autoclave for about 5 days forcrystallization. It is preferred that the crystallization temperature bemaintained below the decomposition temperature of the tetraalkylammoniumcompound. At the completion of the crystallization, the crystallinemolecular sieve is removed from the autoclave, filtered, and washed withwater. The molecular sieve material is dried in a forced draft oven at230° F. (110° C.) for about 16 hours and is then heated in air in amanner such that the temperature rise does not exceed 200° F. (111° C.)per hour until a temperature of about 1,000° F. (538° C.) is reached.Calcination at this temperature is then continued for about 4 hours.

Typically, the surface area of the resulting molecular sieve, asdetermined by BET surface area analysis, is about 350 m² /gm to about390 m² /gm and the sieve particles have a maximum diameter, asdetermined by a scanning electron microscope, of about 2 microns.

Typically, an active hydrocarbon conversion catalyst is prepared byion-exchanging a borosilicate, as prepared above, one or more times withan aqueous solution of ammonium acetate at a temperature of about 185°F. (85° C.) to about 212° F. (100° C.) and drying, as described above,the ion-exchanged molecular sieve. The borosilicate is converted to thehydrogen form by calcination. Then, if desired, the metallic cations,for example, nickel ions, are introduced onto the borosilicate,typically, by exchanging the sieve one or more times with an aqueoussolution of a compound of the metal, for example, nickelous nitrate orthe ammonia complex of nickel, at a temperature of about 185° F. (85°C.) to about 212° F. (100° C.). Subsequently, the catalyst compositionis formed by dispersing the finely-divided metal-exchanged borosilicatein a sol or gel of a high-grade-purity gamma-alumina and adding, whilestirring, a solution of ammonium hydroxide to promote gellation. Theresulting mixture is dried and calcined, as described above, pulverizedto a convenient particle size, and formed into pellets or extrudate.

Alternatively, the original finely-divided un-exchanged crystallineborosilicate can be dispersed in the sol or gel of the refractoryinorganic oxide, such as alumina, the mixture gelled, dried, andcalcined, and the cation-exchanging performed prior to or after thedrying and/or calcination.

In an alternate method, the catalyst composition can be formed bymulling spray-dried alumina with 5 to 20 wt.% gamma-alumina hydrosol orbeta-alumina trihydrate and with the finely-divided borosilicate to forma mixture that is suitable for extruding, adding water to the mixture,if needed, to provide an extrudate having about 20 wt.% to about 50 wt.%water, extruding, drying, and calcining.

Of course, a desired hydrogenation metal can be impregnated onto any ofthe above three compositions.

A broad embodiment of the crystalline borosilicate that is employed inthe catalytic composition of the present invention is a crystallineborosilicate which comprises a molecular sieve material having thefollowing composition in terms of mole ratios of oxides:

    0.9±0.2M.sub.2/n O:B.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O,

wherein M is at least one cation having a valence of n, Y is between 4and about 600, and Z is between 0 and about 160.

In another embodiment, the borosilicate is a crystalline borosilicatewhich comprises a molecular sieve material having the followingcomposition in terms of mole ratios of oxides:

    0.9±0.2M.sub.2/n O:B.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O,

wherein M is at least one cation having a valence of n, Y is between 4and about 600, and Z is between 0 and about 160, and providing an X-raydiffraction pattern comprising the following X-ray diffraction lines andassigned strengths:

    ______________________________________                                        d(A)            Assigned Strength                                             ______________________________________                                        11.2 ± 0.2   W- VS                                                         10.0 ± 0.2   W- MS                                                         5.97 ± 0.07  W- M                                                          3.82 ± 0.05  VS                                                            3.70 ± 0.05  MS                                                            3.62 ± 0.05  M- MS                                                         2.97 ± 0.02  W- M                                                          1.99 ± 0.02  VW- M                                                         ______________________________________                                    

Broadly, according to the present invention, there is provided acatalytic composition which comprises a crystalline borosilicate and aporous refractory inorganic oxide, said borosilicate and said inorganicoxide having been intimately admixed with one another, said borosilicatecomprising a molecular sieve material having the following compositionin terms of mole ratios of oxides:

    0.9±0.2M.sub.2/n O:B.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O,

wherein M is at least one cation having a valence of n, Y is between 4and about 600, and Z is between 0 and about 160.

In one embodiment of the catalytic composition of the present invention,there is provided a catalytic composition which comprises a crystallineborosilicate and a porous refractory inorganic oxide, said borosilicateand said inorganic oxide having been intimately admixed with oneanother, said borosilicate comprising a molecular sieve material havingthe following composition in terms of mole ratios of oxides:

    0.9±0.2M.sub.2/n O:B.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O,

wherein M is at least one cation having a valence of n, Y is between 4and about 600, and Z is between 0 and about 160, and said borosilicateproviding an X-ray diffraction pattern comprising the following X-raydiffraction lines and assigned strengths:

    ______________________________________                                        d(A)            Assigned Strength                                             ______________________________________                                        11.2 ± 0.2   W- VS                                                         10.0 ± 0.2   W- MS                                                         5.97 ± 0.07  W- M                                                          3.82 ± 0.05  VS                                                            3.70 ± 0.05  MS                                                            3.62 ± 0.05  M- MS                                                         2.97 ± 0.02  W- M                                                          1.99 ± 0.02  VW- M                                                         ______________________________________                                    

In another embodiment, there is provided a catalytic composition whichcomprises a crystalline borosilicate and a porous refractory inorganicoxide, said borosilicate and said inorganic oxide having been intimatelyadmixed with one another after said borosilicate has been calcined, andsaid borosilicate comprising a molecular sieve material providing anX-ray diffraction pattern comprising the following X-ray diffractionlines and assigned strengths:

    ______________________________________                                        d(A)            Assigned Strength                                             ______________________________________                                        11.2 ± 0.2   W- VS                                                         10.0 ± 0.2   W- MS                                                         5.97 ± 0.07  W- M                                                          3.82 ± 0.05  VS                                                            3.70 ± 0.05  MS                                                            3.62 ± 0.05  M- MS                                                         2.97 ± 0.02  W- M                                                          1.99 ± 0.02  VW- M                                                         ______________________________________                                    

and having the following composition in terms of mole ratios of oxides:

    0.9±0.2M.sub.2/n O:B.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O,

wherein M is at least one cation having a valence of n, Y is between 4and about 600, and Z is between 0 and about 160.

In still another embodiment of the catalytic composition of the presentinvention, there is provided a catalytic composition which comprises atleast one catalytically-active metal and a catalytic support comprisinga crystalline borosilicate suspended in and distributed throughout amatrix of a refractory inorganic oxide, which composition has beenprepared by the method which comprises: (1) admixing said borosilicatein a finely-divided state with a hydrosol, sol, or hydrogel of saidinorganic oxide in order to uniformly disperse said borosilicate in saidhydrosol, sol, or hydrogel of said inorganic oxide to form an admixture,said borosilicate comprising a molecular sieve material having thefollowing composition in terms of mole ratios of oxides:

    0.9±0.2M.sub.2/n O:B.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O,

wherein M is at least one cation, n is the valence of the cation, Y is avalue within the range of 4 to about 600, and Z is a value within therange of 0 to about 160; (2) while continually stirring the admixture,adding a gelling medium to promote gellation and to form a gel; (3)drying said gel at a temperature of about 77° F. (25° C.) to about 392°F. (200° C.) for a period of about 10 minutes to about 100 hours in thepresence of air to form a dried mixture; (4) calcining said driedmixture by heating said dried mixture in air at a maximum rate of about200° F. per hour (111° C. per hour) to a calcination temperature withinthe range of about 752° F. (400° C.) to about 1,112° F. (600° C.) andmaintaining said dried material at said calcination temperature for aperiod of about 30 minutes to about 20 hours to provide a calcinedcatalytic support material; (5) impregnating said calcined catalyticsupport material with an aqueous solution of a heat-decomposablecompound of said catalytically-active metal to provide an impregnatedmaterial; (6) drying said impregnated material at a temperature of about77° F. (25° C.) to about 392° F. (200° C.) for a period of about 10minutes to about 100 hours in air to obtain a dried impregnatedmaterial; and (7) calcining said dried impregnated material by heatingsaid dried impregnated material in air at a maximum rate of about 200°F. per hour (111° C. per hour) to a calcination temperature within therange of about 752° F. (400° C.) to about 1,112° F. (600° C.) andmaintaining said dried impregnated material at said calcinationtemperature for a period of about 30 minutes to about 20 hours toprovide said catalytic composition.

Moreover, according to the present invention, there is provided a methodfor the preparation of a catalytic composition that is suitable for theconversion of hydrocarbon streams, which method comprises: (1) admixinga crystalline borosilicate in a finely-divided state with a refractoryinorganic oxide to form a catalytic support material, said catalyticsupport material having said borosilicate suspended in and distributedthroughout a matrix of said inorganic oxide, said borosilicatecomprising a molecular sieve material having the following compositionin terms of mole ratios of oxides:

    0.9±0.2M.sub.2/n O:B.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O,

wherein M is at least one cation, n is the valence of the cation, Y is avalue within the range of 4 to about 600, and Z is a value within therange of 0 to about 160; (2) impregnating said catalytic supportmaterial with a solution of a heat-decomposable compound of acatalytically-active metal to provide an impregnated material; (3)drying said impregnated material at a temperature of about 77° F. (25°C.) to about 392° F. (200° C.) for a period of about 10 minutes to about100 hours in moving air to obtain a dried impregnated material; and (4)calcining said dried impregnated material at a temperature within therange of about 752° F. (400° C.) to about 1,112° F. (600° C.) for aperiod of about 30 minutes to about 20 hours to provide said catalyticcomposition.

The catalytic support material can be prepared by either of two methods.In one, wherein the inorganic oxide is an alumina, the catalytic supportmaterial is prepared by: (1) admixing said borosilicate in afinely-divided state with said alumina by mulling spray-dried aluminawith 5 to 20 wt.% gamma-alumina hydrosol or beta-alumina trihydrate andwith said borosilicate to form a mixture that is suitable for extruding;(2) adding water in an amount that will yield an extrudate having about20 wt.% to about 50 wt.% water; (3) adding, if needed, an extrusion aidand a pore-diameter modifier; (4) extruding said resulting admixture toform an extruded admixture; (5) drying said extruded admixture in air ata temperature of about 77° F. (25° C.) to about 392° F. (200° C.) for aperiod of about 10 minutes to about 20 hours to obtain a driedextrudate; and (6) calcining said dried extrudate at a temperaturewithin the range of about 752° F. (400° C.) to about 1,112° F. (600° C.)for a period of about 30 minutes to about 20 hours to provide a calcinedcatalytic support material.

In the other method, the catalytic support material is prepared by: (1)admixing said borosilicate in a finely-divided state with a hydrosol,sol, or hydrogen of said inorganic oxide in order to uniformly dispersesaid borosilicate in said hydrosol, sol, or hydrogen of said inorganicoxide to form an admixture; (2) while continually stirring theadmixture, adding a gelling medium to promote gellation and to form agel; (3) drying said gel at a temperature within the range of about 77°F. (25° C.) to about 392° F. (200° C.) for a period of about 10 minutesto about 100 hours in air to form a dried mixture; and (4) calciningsaid dried mixture at a temperature within the range of about 752° F.(400° C.) to about 1,112° F. (600° C.) for a period of about 20 minutesto about 20 hours to provide a calcined catalytic support material.

The catalytic composition of the present invention can be used for theconversion of hydrocarbon streams. Therefore, there is provided aprocess for the conversion of a hydrocarbon stream, which processcomprises contacting said stream at conversion conditions with thecatalytic composition of the present invention. More particularly, thereis provided a process for the catalytic isomerization of a xylene feed,which process comprises contacting said feed at isomerization conditionswith the catalytic composition of the present invention. Suitableisomerization conditions are listed hereinabove.

Accordingly, there is provided a process for the conversion of ahydrocarbon stream, which process comprises contacting said stream atconversion conditions with a catalytic composition comprising acrystalline borosilicate and a porous refractory inorganic oxide, saidborosilicate and said inorganic oxide having been intimately admixedwith one another, said borosilicate comprising a molecular sievematerial having the following composition in terms of mole ratios ofoxides:

    0.9±0.2 M.sub.2/n O:B.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O

wherein M is at least one cation having a valence of n, Y is between 4and about 600, and Z is between 0 and about 160.

In another embodiment of the process of the present invention, there isprovided a process for the conversion of a hydrocarbon stream, whichprocess comprises contacting said stream at conversion conditions with acatalytic composition comprising at least one catalytically-active metaland a catalytic support comprising a crystalline borosilicate suspendedin and distributed throughout a matrix of a refractory inorganic oxide,which composition has been prepared by the method which comprises: (1)admixing said borosilicate in a finely-divided state with a hydrosol,sol, or hydrogel of said inorganic oxide in order to uniformly dispersesaid borosilicate in said hydrosol, sol, or hydrogel of said inorganicoxide to form an admixture, said borosilicate comprising a molecularsieve material having the following composition in terms of mole ratiosof oxides:

    0.9±0.2 M.sub.2/n O:B.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O,

wherein M is at least one cation, n is the valence of the cation, Y is avalue within the range of 4 to about 600, and Z is a value within therange of 0 to about 160; (2) while continually stirring the admixture,adding a gelling medium to promote gellation and to form a gel; (3)drying said gel at a temperature of about 77° F. (25° C.) to about 392°F. (200° C.) for a period of about 10 minutes to about 100 hours in thepresence of air to form a dried mixture; (4) calcining said driedmixture by heating said dried mixture in air at a maximum rate of about200° F. per hour (111° C. per hour) to a calcination temperature withinthe range of about 752° F. (400° C.) to about 1,112° F. (600° C.) andmaintaining said dried material at said calcination temperature for aperiod of about 30 minutes to about 20 hours to provide a calcinedcatalytic support material; (5) impregnating said calcined catalyticsupport material with a solution of a heat-decomposable compound of saidcatalytically-active metal to provide an impregnated material; (6)drying said impregnated material at a temperature of about 77° F. (25°C.) to about 392° F. (200° C.) for a period of about 10 minutes to about100 hours in air to obtain a dried impregnated material; and (7)calcining said dried impregnated material by heating said driedimpregnated material in air at a maximum rate of about 200° F. per hour(111° C. per hour) to a calcination temperature within the range ofabout 752° F. (400° C.) to about 1,112° F. (600° C.) and maintainingsaid dried impregnated material at said calcination temperature for aperiod of about 30 minutes to about 20 hours to provide said catalyticcomposition.

There is also provided a process for the catalytic isomerization of axylene feed, which process comprises contacting said feed atisomerization conditions with a catalytic composition comprising acrystalline borosilicate and a porous refractory inorganic oxide, saidborosilicate and said inorganic oxide having been intimately admixedwith one another, said borosilicate comprising a molecular sievematerial having the following composition in terms of mole ratios ofoxides:

    0.9±0.2 M.sub.2/n O:B.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O,

wherein M is at least one cation having a valence of n, Y is between 4and about 600, and Z is between 0 and about 160.

Another embodiment of a process of the present invention is a processfor the catalytic isomerization of a xylene feed, which processcomprises contacting said feed at isomerization conditions with acatalytic composition comprising at least one catalytically-active metaland a catalytic support comprising a crystalline borosilicate suspendedin and distributed throughout a matrix of a refractory inorganic oxide,which composition has been prepared by the method which comprises: (1)admixing said borosilicate in a finely-divided state with a hydrosol,sol, or hydrogel of said inorganic oxide in order to uniformly dispersesaid borosilicate in said hydrosol, sol, or hydrogel of said inorganicoxide to form an admixture, said borosilicate comprising a molecularsieve material having the following composition in terms of mole ratiosof oxides:

    0.9±0.2 M.sub.2/n O:B.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O,

wherein M is at least one cation, n is the valence of the cation, Y is avalue within the range of 4 to about 600, and Z is a value within therange of 0 to about 160; (2) while continually stirring the admixture,adding a gelling medium to promote gellation and to form a gel; (3)drying said gel at a temperature of about 77° F. (25° C.) to about 392°F. (200° C.) for a period of about 10 minutes to about 100 hours in thepresence of air to form a dried mixture; (4) calcining said driedmixture by heating said dried mixture in air at a maximum rate of about200° F. per hour (111° C. per hour) to a calcination temperature withinthe range of about 752° F. (400° C.) to about 1,112° F. (600° C.) andmaintaining said dried material at said calcination temperature for aperiod of about 30 minutes to about 20 hours to provide a calcinedcatalytic support material; (5) impregnating said calcined catalyticsupport material with a solution of a heat-decomposable compound of saidcatalytically-active metal to provide an impregnated material; (6)drying said impregnated material at a temperature of about 77° F. (25°C.) to about 392° F. (200° C.) for a period of about 10 minutes to about100 hours in air to obtain a dried impregnated material; and (7)calcining said dried impregnated material by heating said driedimpregnated material in air at a maximum rate of about 200° F. per hour(111° C. per hour) to a calcination temperature within the range ofabout 752° F. (400° C.) to about 1,112° F. (600° C.) and maintainingsaid dried impregnated material at said calcination temperature for aperiod of about 30 minutes to about 20 hours to provide said catalyticcomposition.

The following examples are presented to facilitate an understanding ofthe present invention. They are presented for the purpose ofillustration only and are not intended to limited the scope of thepresent invention.

EXAMPLE I

The AMS-1B crystalline borosilicate was prepared by dissolving 0.25 gmof H₃ BO₃ and 1.6 gm of NaOH in 60 gm of distilled H₂ O. Then 9.4 gms oftetra-n-propylammonium bromide (TPAB) were added and again dissolved.Finally, 12.7 gm of Ludox AS-30 (30% solids) were added with vigorousstirring. The addition of Ludox gave a curdy, gelatinous, milkysolution. This solution was placed in a crystallization vessel andsealed. The vessel was placed in a 329° F. (165° C.) oven and left therefor 7 days. At the end of this time, it was opened and its contents werefiltered. The recovered crystalline material was washed with copiousquantities of H₂ O and was then dried at 329° F. (165° C.) in a forcedair oven. The dried material was identified by X-ray diffraction as acrystalline material having the typical AMS-1B pattern with 100%crystallinity. Its X-ray diffraction pattern is reported in Table IIIabove. The yield was approximately 2 grams.

EXAMPLE II

In this example, the AMS-1B crystalline borosilicate of Example I wasused to produce a catalyst having isomerization capabilities.

The material from Example I was calcined at 1,100° F. (593° C.) in airfor 4 hours to remove the organic base. The calcined sieve was exchangedone time with a solution of 20 gm of NH₄ NO₃ in 200 ml of H₂ O and thena second time with 20 gm of ammonium acetate in 200 ml of H₂ O at 190°F. (88° C.) for 2 hours. The exchanged borosilicate was dried andcalcined in air by heating it to 900° F. (482° C.) in 4 hours,maintaining the borosilicate at 900° F. (482° C.) for 4 hours, and thencooling to 100° F. (38° C.) in 4 hours. The calcined material wasexchanged with 100 ml of a 5% Ni(NO₃)₂.6H₂ O solution for 2 hours at190° F. (88° C.). The sieve was washed with H₂ O and the Ni(NO₃)₂solution was apparently washed from the sieve. The sieve was dried andcalcined again using the above procedure. About 2 grams of theborosilicate were dispersed in 16.9 gm of PHF-Al₂ O₃ (a gamma-alumina)hydrosol (8.9% solids) and mixed thoroughly. One ml of distilled H₂ Oand 1 ml of concentrated NH₄ OH were mixed and added to the slurry withintensive mixing. The AMS-1B-Al₂ O₃ mix was placed in a drying oven at329° F. (165° C.) for 4 hours. The dried material was again calcined,using the above procedure. The calcined catalyst was crushed to a30-to-50-mesh material, i.e., material that would pass through a 30-meshscreen (U.S. Sieve Series), but be retained on a 50-mesh screen (U.S.Sieve Series), and impregnated with 2 ml of a solution of 5%Ni(NO₃)₂.6H₂ O in distilled H₂ O. The catalyst was again dried andactivated by a fourth programmed calcination.

The calcined catalyst contained 65 weight percent borosilicate and 35weight percent amorphous alumina with approximately 0.5 weight percentof the total solid as nickel. This material was analyzed by X-raydiffraction and the results are reported in Table I above. The amorphousalumina did not significantly alter the diffraction pattern generated.

One gram of the sized and activated catalyst, identified hereinafter asCatalyst A, was placed in the microreactor and sulfided with H₂ S for 20minutes at room temperature. The catalyst was then placed under H₂pressure and heated to 600° F. (316° C.). After 1 hour, feed was passedthrough the microreactor under the following once-through conditions:

    ______________________________________                                        Temperature        800° F. (427° C.)                            Pressure           150 psig (1,138 KPa)                                       WHSV               6.28 hrs..sup.-1                                           H/HC, mole ratio   7                                                          ______________________________________                                    

The liquid feed and effluent streams for this operation are shown below.Because of the equipment limitations on the screening unit, analyses onliquid streams only were performed and reported. The lightenedproduction over this catalyst was low from the gas chromatographicanalysis made on the off-gas stream from the unit. The volume of off-gaswas determined to not substantially reduce overall liquid yields overthe catalyst.

    ______________________________________                                        Component Liquid Feed, wt. %                                                                           Liquid Product, wt. %                                ______________________________________                                        Paraffins and                                                                            0.03          0.08                                                 naphthenes                                                                    Benzene   --             1.51                                                 Toluene   0.077          0.26                                                 Ethylbenzene                                                                            19.71          17.35                                                para-Xylene                                                                             --             19.43                                                meta-Xylene                                                                             79.80          46.40                                                ortho-Xylene                                                                             0.38          14.96                                                C.sub.9 +*                                                                              --             1.*                                                  ______________________________________                                         *Approximate values only.                                                

In addition, more detailed and comprehensive analyses of the productswere obtained. These are presented hereinbelow in Table IX. The hours onoil for each sample were the sum total of hours from the beginning ofthe test to the end of the period during which the sample was taken. Theterm "PATE" represents "percent approach to equilibrium," which has beencalculated for each xylene isomer.

                                      TABLE IX                                    __________________________________________________________________________    XYLENE ISOMERIZATION WITH CATALYST A                                          TEST NO. 1                                                                    Sample No.  Feed                                                                             3  4  5  6  9   10 11 12 13 16 17 18 19 20  21                 __________________________________________________________________________    Reactor Temp., ° F.                                                                   640                                                                              680                                                                              720                                                                              760                                                                              800 800                                                                              800                                                                              800                                                                              800                                                                              801                                                                              801                                                                              724                                                                              721                                                                              800 801                ° C.    338                                                                              360                                                                              382                                                                              404                                                                              427 427                                                                              427                                                                              427                                                                              427                                                                              428                                                                              428                                                                              384                                                                              383                                                                              427 428                Reactor Press., psig                                                                         150                                                                              150                                                                              150                                                                              150                                                                              150 150                                                                              150                                                                              150                                                                              150                                                                              150                                                                              150                                                                              150                                                                              150                                                                              150 150                KPa            1,138                                                                            1,138                                                                            1,138                                                                            1,138                                                                            1,138                                                                             1,138                                                                            1,138                                                                            1,138                                                                            1,138                                                                            1,138                                                                            1,138                                                                            1,138                                                                            1,138                                                                            1,138                                                                             1,138              H.sub.2 Flow, ft.sup.3 /hr                                                                   0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3 0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3 0.3                m.sup.3 /hr    0.009                                                                            0.009                                                                            0.009                                                                            0.009                                                                            0.009                                                                             0.009                                                                            0.009                                                                            0.009                                                                            0.009                                                                            0.009                                                                            0.009                                                                            0.009                                                                            0.009                                                                            0.009                                                                             0.009              Feed Rate, gm/hr                                                                             7.48                                                                             8.53                                                                             9.14                                                                             8.58                                                                             6.28                                                                              8.20                                                                             5.47                                                                             5.53                                                                             6.23                                                                             6.71                                                                             6.19                                                                             6.29                                                                             4.88                                                                             6.63                                                                              5.00               Product Analysis, wt. %                                                       Paraffins + Naphthenes                                                                    -- 0.066                                                                            0.33                                                                             0.17                                                                             -- 0.09                                                                              0.12                                                                             -- 0.06                                                                             0.09                                                                             0.06                                                                             0.07                                                                             0.05                                                                             0.07                                                                             0.14                                                                              0.06               Benzene     -- 0.107                                                                            0.28                                                                             0.58                                                                             0.90                                                                             1.79                                                                              1.55                                                                             1.64                                                                             3.09                                                                             3.00                                                                             1.61                                                                             1.33                                                                             0.52                                                                             0.70                                                                             1.45                                                                              1.87               Toluene      0.03                                                                            0.154                                                                            0.26                                                                             0.20                                                                             0.24                                                                             0.31                                                                              0.25                                                                             0.28                                                                             0.48                                                                             0.46                                                                             0.25                                                                             0.20                                                                             0.13                                                                             0.16                                                                             0.22                                                                              0.31               Ethylbenzene (EB)                                                                         20.97                                                                            20.30                                                                            19.94                                                                            19.58                                                                            19.1                                                                             17.9                                                                              18.3                                                                             18.1                                                                             16.4                                                                             16.4                                                                             17.1                                                                             17.6                                                                             19.3                                                                             18.8                                                                             17.8                                                                              17.1               p-Xylene (pX)                                                                             -- 11.38                                                                            14.31                                                                            18.45                                                                            19.2                                                                             20.8                                                                              20.2                                                                             20.7                                                                             21.0                                                                             21.1                                                                             19.2                                                                             14.5                                                                             16.3                                                                             17.8                                                                             18.5                                                                              19.3               m-Xylene (mX)                                                                              78.5                                                                            62.49                                                                            57.60                                                                            50.57                                                                            49.0                                                                             44.2                                                                              45.9                                                                             45.0                                                                             42.4                                                                             42.4                                                                             45.5                                                                             51.3                                                                             52.7                                                                             49.4                                                                             46.8                                                                              44.3               o-Xylene (oX)                                                                             -- 5.44                                                                             7.28                                                                             10.46                                                                            11.5                                                                             14.9                                                                              13.7                                                                             14.3                                                                             16.6                                                                             16.5                                                                             15.2                                                                             14.2                                                                             10.4                                                                             12.3                                                                             14.2                                                                              16.0               C.sub.9 +    0.5                                                                             -- -- -- -- --  -- -- -- -- 1.18                                                                             0.80                                                                             0.60                                                                             0.66                                                                             0.90                                                                              1.08               Calculated Results                                                            ppH.sub.2, psia                                                                              140.5                                                                            137.7                                                                            136.1                                                                            137.6                                                                            143.9                                                                             138.6                                                                            146.3                                                                            146.1                                                                            144.1                                                                            144.2                                                                            144.2                                                                            143.9                                                                            147.1                                                                            142.9                                                                             147.7              H/HC           5.8                                                                              5.1                                                                              4.8                                                                              5.1                                                                              6.9 5.3                                                                              8.0                                                                              7.9                                                                              7.0                                                                              7.0                                                                              7.0                                                                              6.9                                                                              8.4                                                                              6.6 8.7                Contact Time, Sec                                                                            3.03                                                                             2.87                                                                             2.74                                                                             2.68                                                                             2.71                                                                              2.61                                                                             2.76                                                                             2.75                                                                             2.71                                                                             2.72                                                                             2.72                                                                             2.89                                                                             2.96                                                                             2.69                                                                              2.78               WHSV, hr.sup.-1                                                                              7.48                                                                             8.53                                                                             9.14                                                                             8.58                                                                             6.28                                                                              8.20                                                                             5.47                                                                             5.53                                                                             6.23                                                                             6.71                                                                             6.19                                                                             6.29                                                                             4.88                                                                             6.63                                                                              5.00               pX PATE, %     60.5                                                                             76.4                                                                             98.4                                                                             102.5                                                                            111.06                                                                            108.0                                                                            110.4                                                                            111.6                                                                            112.5                                                                            102.6                                                                            76.8                                                                             86.6                                                                             94.9                                                                             99.1                                                                              103.4              mX PATE, %     44.6                                                                             57.4                                                                             76.5                                                                             80.7                                                                             93.3                                                                              88.6                                                                             91.3                                                                             98.2                                                                             98.2                                                                             89.7                                                                             74.4                                                                             70.3                                                                             79.5                                                                             85.6                                                                              92.6               oX PATE, %     28.16                                                                            37.9                                                                             54.4                                                                             59.0                                                                             75.9                                                                              69.7                                                                             72.7                                                                             84.7                                                                             84.1                                                                             77.2                                                                             72.2                                                                             54.1                                                                             64.1                                                                             72.5                                                                              81.9               EB Conversion, %                                                                             3.2                                                                              4.9                                                                              6.6                                                                              8.9                                                                              14.6                                                                              12.7                                                                             13.7                                                                             21.8                                                                             21.8                                                                             18.5                                                                             16.1                                                                             8.0                                                                              10.3                                                                             15.1                                                                              18.5               Time on Oil, hrs                                                                             16.5                                                                             22.5                                                                             40.5                                                                             47.5                                                                             136.5                                                                             145.6                                                                            160.5                                                                            168.5                                                                            184.5                                                                            223.0                                                                            238.5                                                                            245.5                                                                            309.0                                                                            317.01                                                                            333.0              __________________________________________________________________________

EXAMPLE III

In this example, another AMS-1B borosilicate was prepared. A solutionwas prepared by dissolving 2.5 gm of H₃ BO₃ and 7.5 gm of NaOH in 600 gmof distilled water. Then 94.3 gm of tetrapropylammonium bromide wasdissolved in the solution. To the solution was added 114.5 gm of LudoxHS-30 and the resulting mixture was thoroughly blended. It wassubsequently transferred to a 1-liter crystallizer. Crystallization wascarried out at a temperature of 329° F. (165° C.) and a pressure ofabout 105 psig (827 KPa) for 7 days. The solid material was filteredfrom the crystallization solution and washed with approximately 1 literof distilled water. The washed material was dried in a forced draftdrying oven at a temperature of 329° F. (165° C.) overnight(approximately 16 hours). The dried material, which weighed 35.6 gm, wastransferred to a calcining furnace, where it was calcined at atemperature of 1,000° F. (538° C.) for 4 hours after it had been heatedfor 4.5 hours such that the temperature increased at a rate of 200° F.per hour (111° C. per hour) to the 1,000° F. (538° C.).

A 20-gm portion of the calcined material, identified as crystallineAMS-1B borosilicate by its X-ray diffraction pattern, was slurried in asolution that had been prepared by dissolving 30 gm of ammonium acetatein 300 gm of distilled water. This ammonium cation-exchange was carriedout for 1.5 hrs at a temperature of 194° F. (90° C.). After thisexchange had been completed, the borosilicate was filtered from thesolution and washed with 150 ml of distilled water. The exchangeprocedure was repeated 4 times. After the last exchange and subsequentwash, the borosilicate was filter dried and then transferred to acalcining furnace. The furnace was held at a temperature of 250° F.(121° C.) for 3 hrs before the borosilicate was calcined under atemperature control program at a temperature of 900° F. (482° C.) for 4hrs. During the program, 3.25 hrs were used to increase the temperaturein a linear manner from 250° F. (121° C.) to a temperature of 900° F.(482° C.). The furnace was held at a temperature of 900° F. (482° C.)for 4 hrs, and a minimum of 3.25 hrs was required to cool the materialfrom 900° F. (482° C.) to a temperature of 250° F. (121° C.). Thecalcined material was the hydrogen form of the borosilicate.

The resulting hydrogen form of the borosilicate was subsequentlyexchanged with a nickel nitrate solution. For this latter cationexchange, 150 ml of a 5% solution was employed. The exchange was carriedout at a temperature of 194° F. (90° C.) for a period of 1.5 hrs. Thesolution was prepared by dissolving 7.5 gm of Ni(NO₃)₂.6H₂ O indistilled water. The exchanged borosilicate was filtered from theexchange solution, washed with 150 ml of distilled water, and filterdried. The material was then dried at a temperature of 329° F. (165° C.)for 3 hrs in a forced draft drying oven and then calcined according tothe above-described program at a temperature of 900° F. (482° C.) for 4hrs. The resultant borosilicate was then in the nickel- andhydrogen-form and weighed 19.2 gm.

A catalyst support was prepared by thoroughly dispersing the abovenickel- and hydrogen-form of borosilicate in 118.7 gm of a PHF-aluminahydrosol (8.7% solids), which hydrosol was obtained from the AmericanCyanamid Company. The hydrosol-borosilicate blend was subsequentlygelled by adding a solution that had been prepared by mixing 7.5 ml ofconcentrated ammonium hydroxide and 7.5 ml of distilled water. Theresulting gel was dried for 4 hrs at a temperature of 329° F. (165° C.)in the forced draft drying oven. The sol was then transferred to thedrying oven, which was maintained at a temperature of 250° F. (121° C.)for 3 hrs and then subjected to a programmed calcination, as describedhereinabove. The calcined material was pulverized and sieved to obtain a30-to-50-mesh material (U.S. Sieve Series), i.e., material that wouldpass through a 30-mesh screen (U.S. Sieve Series) but be retained upon a50-mesh screen (U.S. Sieve Series). This 30-to-50-mesh material wasimpregnated with 11.5 ml of a 5% Ni(NO₃)₂.6H₂ O solution, which had beenprepared by dissolving the Ni(NO₃)₂.6H₂ O in sufficient distilled water.The resulting impregnated material was subjected to a final calcinationwith a 900° F. (482° C.) calcination program, but the material was driedfor a period of 5 hrs at a temperature of 250° F. (121° C.), rather thanat a period of 3 hrs for such drying. As the material was being dried atthe temperature of 250° F. (121° C.), it was stirred frequently tofacilitate an even drying. The finished catalyst, i.e., the calcinedcatalyst, is hereinafter identified as Catalyst B.

The activated Catalyst B was tested for its ability to isomerizexylenes. A 1-gm portion of the activated Catalyst B was placed in amicroreactor and sulfided with pure H₂ S for 15 minutes at roomtemperature. The flow rate of H₂ S was approximately 0.3 ft³ /hr (0.009m³ /hr). The catalyst was then placed under H₂ pressure and heated to atemperature of 800° F. (427° C.). After 1 hr, a synthetic xyleneisomerization feed was passed through the microreactor under theconditions specified in the following Table X. The test results obtainedfrom this test, Test No. 2, are presented hereinbelow in Table X. Theresults obtained for this test were obtained from Analytical Services.The time on oil for a particular sample is a sum of the hours on oilincluding the complete amount of time during which that particularsample was taken.

                                      TABLE X                                     __________________________________________________________________________    XYLENE ISOMERIZATION WITH CATALYST B                                          TEST NO. 2                                                                    Sample No.  Feed                                                                              2  3  4  5  6  7  8  9                                        __________________________________________________________________________    Reactor Temp., ° F.                                                                    800                                                                              840                                                                              840                                                                              840                                                                              800                                                                              800                                                                              800                                                                              800                                      ° C.     427                                                                              449                                                                              449                                                                              449                                                                              427                                                                              427                                                                              427                                                                              427                                      Reactor Press., psig                                                                          150                                                                              150                                                                              150                                                                              150                                                                              150                                                                              150                                                                              150                                                                              150                                      KPa             1,138                                                                            1,138                                                                            1,138                                                                            1,138                                                                            1,138                                                                            1,138                                                                            1,138                                                                            1,138                                    H.sub.2 Rate, ft.sup.3 /hr                                                                    0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3                                      m.sup.3 /hr     0.009                                                                            0.009                                                                            0.009                                                                            0.009                                                                            0.009                                                                            0.009                                                                            0.009                                                                            0.009                                    Feed Rate, gm/hr                                                                              7.80                                                                             6.28                                                                             7.62                                                                             9.91                                                                             6.67                                                                             5.61                                                                             5.37                                                                             5.08                                     Product Analysis, wt. %                                                       Paraffins + Naphthenes                                                                    0.05                                                                              0.12                                                                             0.10                                                                             0.04                                                                             0.02                                                                             0.02                                                                             0.03                                                                             0.03                                                                             0.02                                     Benzene     --  1.28                                                                             2.76                                                                             2.42                                                                             2.59                                                                             1.42                                                                             1.38                                                                             1.30                                                                             1.29                                     Toluene     0.07                                                                              0.28                                                                             0.51                                                                             0.51                                                                             0.46                                                                             0.23                                                                             0.21                                                                             0.20                                                                             0.20                                     Ethylbenzene (EB)                                                                         19.56                                                                             16.92                                                                            14.88                                                                            15.14                                                                            14.68                                                                            16.62                                                                            16.63                                                                            16.71                                                                            16.78                                    p-Xylene (pX)                                                                             8.65                                                                              16.40                                                                            18.45                                                                            18.35                                                                            18.42                                                                            16.99                                                                            17.46                                                                            17.30                                                                            17.38                                    m-Xylene (mX)                                                                             47.83                                                                             42.87                                                                            41.74                                                                            41.60                                                                            41.49                                                                            42.28                                                                            42.12                                                                            42.20                                                                            42.09                                    o-Xylene (oX)                                                                             23.66                                                                             21.21                                                                            20.13                                                                            20.31                                                                            20.21                                                                            21.11                                                                            20.99                                                                            21.19                                                                            21.15                                    C.sub.9 +   0.22                                                                              0.92                                                                             1.43                                                                             1.61                                                                             2.11                                                                             1.33                                                                             1.18                                                                             1.07                                                                             1.09                                     Diethylbenzene                                                                            --  0.40                                                                             0.59                                                                             0.72                                                                             1.04                                                                             0.80                                                                             0.74                                                                             0.68                                                                             0.68                                     Calculated Results                                                            ppH.sub.2, psia 136.8                                                                            141.5                                                                            137.4                                                                            130.8                                                                            140.3                                                                            143.6                                                                            144.4                                                                            145.4                                    H/HC            4.9                                                                              6.1                                                                              5.0                                                                              3.9                                                                              5.7                                                                              6.8                                                                              7.1                                                                              7.5                                      Contact Time, Sec                                                                             2.58                                                                             2.58                                                                             2.51                                                                             2.39                                                                             2.64                                                                             2.71                                                                             2.72                                                                             2.74                                     WHSV, hr.sup.-1 7.80                                                                             6.28                                                                             7.62                                                                             9.91                                                                             6.67                                                                             5.61                                                                             5.37                                                                             5.08                                     pX PATE, %      75.8                                                                             96.8                                                                             96.0                                                                             97.00                                                                            81.8                                                                             86.0                                                                             84.2                                                                             85.1                                     mX PATE, %      84.9                                                                             99.4                                                                             101.2                                                                            101.8                                                                            93.8                                                                             98.1                                                                             97.8                                                                             99.0                                     oX PATE, %      62.1                                                                             92.7                                                                             87.6                                                                             89.3                                                                             63.9                                                                             68.0                                                                             63.9                                                                             64.5                                     EB Conversion, %                                                                              13.5                                                                             23.9                                                                             22.6                                                                             24.9                                                                             15.0                                                                             15.0                                                                             14.6                                                                             14.2                                     Time on Oil, hrs                                                                              23.0                                                                             38.7                                                                             44.0                                                                             60.5                                                                             67.5                                                                             82.75                                                                            90.25                                                                            107.5                                    __________________________________________________________________________

EXAMPLE IV

Another AMS-1B borosilicate was prepared. The following quantities ofchemicals were employed in its preparation: 1,800.0 gm of distilledwater; 120.0 gm of H₃ BO₃ ; 57.0 gm of NaOH; 282.9 gm oftetrapropylammonium bromide; 228.0 gm of Ludox HS-40. The resulting pHof the slurry was 10.6. The borosilicate was crystallized at atemperature of 329° F. (165° C.) for 7 days. The crystallizedborosilicate was then treated as described hereinabove in Example III.After drying, 92.3 gm of the crystalline borosilicate were recovered.The calcined borosilicate was identified by X-ray diffraction analysisas an AMS-1B borosilicate. It was then introduced into a catalyticcomposition in a manner similar to that as described in Example III forthe preparation of Catalyst B. However, several exceptions to the methodof preparation in Example III were employed. These exceptions were: (1)a 50-gm portion of borosilicate was used with 100 gm of ammonium acetatefor each exchange; (2) a 15-gm portion of the exchanged and calcinedhydrogen-form crystalline borosilicate was exchanged with 150 ml of the5% solution of Ni(NO₃)₂.6H₂ O; and (3) a 14.3-gm portion of nickel- andhydrogen-form crystalline borosilicate was dispersed in 88.5 gm ofPHF-alumina hydrosol obtained from the American Cyanamid Company. Thefinished catalyst is hereinafter identified as Catalyst C.

A 1-gm sample of Catalyst C was tested for xylene isomerization asdiscussed hereinabove in Examples II and III. The results of this test,Test No. 3, are presented hereinafter in Table XI.

                                      TABLE XI                                    __________________________________________________________________________    XYLENE ISOMERIZATION WITH CATALYST C                                          TEST NO. 3                                                                    Sample No.  Feed                                                                             1  3  5  6  7  8   9                                           __________________________________________________________________________    Reactor Temp., ° F.                                                                   680                                                                              680                                                                              720                                                                              720                                                                              760                                                                              800 840                                         ° C.    360                                                                              360                                                                              382                                                                              382                                                                              404                                                                              427 449                                         Reactor Press., psig                                                                         150                                                                              150                                                                              150                                                                              150                                                                              150                                                                              150 150                                         KPa            1,138                                                                            1,138                                                                            1,138                                                                            1,138                                                                            1,138                                                                            1,138                                                                             1,138                                       H.sub.2 Rate, ft.sup.3 /hr                                                                   0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3 0.3                                         m.sup.3 /hr    0.009                                                                            0.009                                                                            0.009                                                                            0.009                                                                            0.009                                                                            0.009                                                                             0.009                                       Feed Rate, gm/hr                                                                             2.59                                                                             4.25                                                                             6.29                                                                             6.40                                                                             5.93                                                                             5.57                                                                              5.81                                        Product Analysis, wt. %                                                       Paraffins + Naphthenes                                                                     0.05                                                                            -- -- -- 0.01                                                                             0.01                                                                             0.02                                                                              0.02                                        Benzene     -- 0.30                                                                             0.27                                                                             0.36                                                                             0.34                                                                             0.58                                                                             0.96                                                                              1.65                                        Toluene      0.07                                                                            0.15                                                                             0.14                                                                             0.15                                                                             0.16                                                                             0.23                                                                             0.32                                                                              0.52                                        Ethylbenzene (EB)                                                                         19.56                                                                            18.82                                                                            19.01                                                                            18.83                                                                            18.80                                                                            18.23                                                                            17.66                                                                             16.33                                       p-Xylene (pX)                                                                              8.65                                                                            16.49                                                                            15.71                                                                            16.48                                                                            15.77                                                                            17.99                                                                            18.46                                                                             18.71                                       m-Xylene (mX)                                                                             47.83                                                                            43.77                                                                            44.06                                                                            43.55                                                                            43.89                                                                            42.60                                                                            42.25                                                                             41.63                                       o-Xylene (oX)                                                                             23.66                                                                            20.47                                                                            20.81                                                                            20.63                                                                            20.57                                                                            19.38                                                                            18.77                                                                             18.42                                       C.sub.9.sup.+                                                                              0.22                                                                            -- -- -- 0.46                                                                             0.99                                                                             1.54                                                                              2.71                                        Diethylbenzene                                                                            -- -- -- -- 0.10                                                                             0.19                                                                             0.29                                                                              0.47                                        Calculated Results                                                            ppH.sub.2, psia                                                                              154.3                                                                            143.5                                                                            141.4                                                                            141.0                                                                            142.6                                                                            143.7                                                                             143.0                                       H/HC           14.8                                                                             6.8                                                                              6.1                                                                              5.9                                                                              6.5                                                                              6.8 6.6                                         Contact Time, Sec                                                                            3.21                                                                             2.99                                                                             2.85                                                                             2.84                                                                             2.77                                                                             2.71                                                                              2.61                                        WHSV, hr.sup.-1                                                                              1.45                                                                             4.25                                                                             6.29                                                                             6.40                                                                             5.93                                                                             5.57                                                                              5.81                                        pX PATE, %     74.8                                                                             67.9                                                                             75.3                                                                             69.5                                                                             92.0                                                                             98.24                                                                             103.1                                       mX PATE, %     79.8                                                                             73.3                                                                             80.2                                                                             70.4                                                                             87.5                                                                             86.28                                                                             88.0                                        oX PATE, %     69.0                                                                             61.5                                                                             69.1                                                                             68.2                                                                             98.0                                                                             115.86                                                                            127.5                                       EB Conversion, %                                                                             3.8                                                                              2.8                                                                              3.7                                                                              3.9                                                                              6.8                                                                              9.7 16.5                                        Time on Oil, hrs                                                                             16.0                                                                             40.0                                                                             64.0                                                                             71 88 95  112                                         __________________________________________________________________________

EXAMPLE V

In this example, an impregnated catalytic composition was prepared andtested for its ability to isomerize xylenes. A 2-gm portion of CatalystC was impregnated with a solution of 5% Ni(NO₃)₂.6H₂ O. The solution wasprepared as explained hereinabove. Sufficient solution was employed foran adequate impregnation. The impregnated catalyst was dried in a forceddraft drying oven at a temperature of 329° F. (165° C.) with frequentagitation. The catalyst was given an additional drying step at atemperature of 482° F. (250° C.) prior to being subjected to aprogrammed calcination at 900° F. (482° C.). A 1-gm portion of theimpregnated and calcined catalyst, identified hereinafter as Catalyst D,was tested for its ability to isomerize xylenes. The test procedureemployed in Example II was used. Test results from this test, Test No.4, are presented in Table XII.

An additional test was made with Catalyst D. This test is identifiedhereinafter as Test No. 5. Its results are presented hereinafter inTable XIII.

                                      TABLE XII                                   __________________________________________________________________________    XYLENE ISOMERIZATION WITH CATALYST D                                          TEST NO. 4                                                                    Sample No.   Feed                                                                             1   2   3   4   5   6   7   8   9                             __________________________________________________________________________    Reactor Temp., ° F.                                                                    680 680 640 640 720 720 760 800 840                              ° C.  360 360 338 338 382 382 404 427 449                           Reactor Press., psig                                                                          150 150 150 150 150 150 150 150 150                              KPa          1,138                                                                             1,138                                                                             1,138                                                                             1,138                                                                             1,138                                                                             1,138                                                                             1,138                                                                             1,138                                                                             1,138                         H.sub.2 Rate, ft.sup.3 /hr                                                                    0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3                              m.sup.3 /hr  0.009                                                                             0.009                                                                             0.009                                                                             0.009                                                                             0.009                                                                             0.009                                                                             0.009                                                                             0.009                                                                             0.009                         Feed Rate, gm/hr                                                                              5.28                                                                              6.66                                                                              5.67                                                                              6.71                                                                              6.21                                                                              6.19                                                                              5.42                                                                              6.24                                                                              5.47                          Product Analysis, wt. %                                                       Paraffins + Naphthenes                                                                     0.05                                                                             0.08                                                                              --  --   -- 0.05                                                                              0.06                                                                              --  --  0.02                          Benzene      -- 0.39                                                                              0.37                                                                              0.24                                                                              0.19                                                                              0.51                                                                              0.54                                                                              0.87                                                                              1.26                                                                              2.25                          Toluene      0.07                                                                             0.42                                                                              0.24                                                                              0.16                                                                              0.14                                                                              0.24                                                                              0.24                                                                              0.35                                                                              0.49                                                                              0.78                          Ethylbenzene (EB)                                                                          19.56                                                                            18.87                                                                             18.80                                                                             19.12                                                                             19.10                                                                             18.40                                                                             18.37                                                                             17.64                                                                             16.75                                                                             15.21                         p-Xylene (pX)                                                                              8.65                                                                             18.17                                                                             17.93                                                                             16.39                                                                             16.08                                                                             18.58                                                                             18.77                                                                             19.11                                                                             19.20                                                                             19.08                         m-Xylene (mX)                                                                              47.83                                                                            42.68                                                                             42.94                                                                             43.48                                                                             43.63                                                                             42.69                                                                             42.50                                                                             42.56                                                                             42.48                                                                             42.03                         o-Xylene (oX)                                                                              23.66                                                                            19.39                                                                             19.73                                                                             20.62                                                                             20.88                                                                             18.96                                                                             18.87                                                                             18.47                                                                             18.14                                                                             18.11                         C.sub.9.sup.+                                                                              0.22                                                                             --  --  --  --  0.56                                                                              0.64                                                                              1.00                                                                              1.67                                                                              2.53                          Diethylbenzene                                                                             -- --  --  --  --  0.20                                                                              0.22                                                                              0.36                                                                              0.47                                                                              0.59                          Calculated Results                                                            ppH.sub.2, psia 144.7                                                                             140.3                                                                             143.5                                                                             140.1                                                                             141.7                                                                             141.8                                                                             144.3                                                                             141.6                                                                             144.1                         H/HC            7.2 5.7 6.8 5.7 6.2 6.2 7.1 6.1 7.0                           Contact Time, Sec                                                                             3.01                                                                              2.92                                                                              3.10                                                                              3.02                                                                              2.85                                                                              2.85                                                                              2.81                                                                              2.67                                                                              2.63                          WHSV, hr.sup.-1 5.28                                                                              6.66                                                                              5.63                                                                              6.68                                                                              6.21                                                                              6.19                                                                              5.42                                                                              6.24                                                                              5.47                          pX PATE, %      92.1                                                                              88.99                                                                             73.9                                                                              70.8                                                                              96.6                                                                              98.7                                                                              102.6                                                                             104.8                                                                             105.7                         mX PATE, %      94.8                                                                              93.5                                                                              86.0                                                                              84.2                                                                              91.2                                                                              93.7                                                                              89.7                                                                              85.6                                                                              85.4                          oX PATE, %      88.8                                                                              83.6                                                                              61.3                                                                              56.7                                                                              103.2                                                                             104.6                                                                             120.0                                                                             133.2                                                                             138.4                         EB Conversion, %                                                                              3.5 3.9 2.2 2.3 5.9 6.1 9.8 14.4                                                                              22.2                          Time on Oil, hrs                                                                              16.0                                                                              23.0                                                                              40.0                                                                              47.0                                                                              64.0                                                                              71.0                                                                              88.0                                                                              95.0                                                                              112.0                         __________________________________________________________________________

                                      TABLE XIII                                  __________________________________________________________________________    XYLENE ISOMERIZATION WITH CATALYST D                                          TEST NO. 5                                                                    Sample No.   Feed                                                                             1   2   3   4   5   6   7   8   9                             __________________________________________________________________________    Reactor Temp., °F.                                                                     722 720 720 720 760 760 800 800 840                              °C.   383 382 382 382 404 404 427 427 449                           Reactor Press., psig                                                                          150 150 150 150 150 150 150 150 150                           KPa             1,138                                                                             1,138                                                                             1,138                                                                             1,138                                                                             1,138                                                                             1,138                                                                             1,138                                                                             1,138                                                                             1,138                         H.sub.2 Rate, ft.sup.3 /hr                                                                    0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3                              m.sup.3 /hr  0.009                                                                             0.009                                                                             0.009                                                                             0.009                                                                             0.009                                                                             0.009                                                                             0.009                                                                             0.009                                                                             0.009                         Feed Rate, gm/hr                                                                              2.22                                                                              5.81                                                                              4.78                                                                              6.37                                                                              5.76                                                                              6.50                                                                              4.30                                                                              4.27                                                                              0.71                          Product Analysis, wt.%                                                        Paraffins + Naphthenes                                                                     0.05                                                                             1.24                                                                              --  0.02                                                                              0.03                                                                              0.01                                                                              0.02                                                                              0.01                                                                              0.01                                                                              0.01                          Benzene      -- 0.77                                                                              0.67                                                                              0.65                                                                              0.64                                                                              0.86                                                                              0.93                                                                              1.29                                                                              1.54                                                                              1.45                          Toluene      0.07                                                                             0.52                                                                              0.33                                                                              0.29                                                                              0.29                                                                              0.34                                                                              0.34                                                                              0.46                                                                              0.52                                                                              0.44                          Ethylbenzene (EB)                                                                          19.56                                                                            17.88                                                                             18.46                                                                             18.38                                                                             18.01                                                                             17.62                                                                             17.63                                                                             16.78                                                                             16.70                                                                             15.41                         p-Xylene (pX)                                                                              8.65                                                                             18.98                                                                             19.11                                                                             18.99                                                                             19.02                                                                             --  19.17                                                                             19.07                                                                             19.39                                                                             19.21                         m-Xylene (mX)                                                                              47.83                                                                            42.48                                                                             42.83                                                                             42.88                                                                             42.75                                                                             79.97                                                                             42.46                                                                             42.33                                                                             42.36                                                                             42.47                         o-Xylene (oX)                                                                              23.66                                                                            18.14                                                                             18.60                                                                             18.79                                                                             18.07                                                                             --  18.31                                                                             18.25                                                                             17.95                                                                             18.66                         C.sub.9 +    0.22                                                                             --  --  --  --  1.20                                                                              1.11                                                                              1.82                                                                              1.61                                                                              2.34                          Diethylbenzene                                                                             -- --  --  --  --  0.39                                                                              0.37                                                                              0.52                                                                              0.47                                                                              0.62                          Calculated Results                                                            ppH.sub.2, psia 155.7                                                                             143.0                                                                             146.4                                                                             141.2                                                                             143.1                                                                             140.8                                                                             148.1                                                                             148.2                                                                             161.7                         H/HC            17.3                                                                              6.6 8.0 6.0 6.6 5.9 8.9 9.0 53.7                          Contact Time, Sec                                                                             3.13                                                                              2.88                                                                              2.95                                                                              2.84                                                                              2.78                                                                              2.74                                                                              2.79                                                                              2.79                                                                              2.75                          WHSV, hr.sup.-1 2.22                                                                              5.81                                                                              4.75                                                                              6.37                                                                              5.76                                                                              6.50                                                                              4.30                                                                              4.24                                                                              .71                           pX PATE, %      102.0                                                                             101.1                                                                             99.6                                                                              100.4                                                                             --  103.68                                                                            103.9                                                                             106.5                                                                             104.3                         mX PATE, %      88.8                                                                              91.6                                                                              91.9                                                                              92.1                                                                              --  89.61                                                                             86.5                                                                              85.9                                                                              88.0                          oX PATE, %      118.2                                                                             112.6                                                                             109.0                                                                             110.5                                                                             --  122.5                                                                             129.6                                                                             136.9                                                                             130.7                         EB Conversion, %                                                                              8.6 5.6 6.0 4.9 9.9 9.9 14.2                                                                              14.6                                                                              21.2                          Time on Oil, hrs                                                                              16.0                                                                              23.0                                                                              40.0                                                                              47.0                                                                              64.0                                                                              71.0                                                                              88.0                                                                              95.0                                                                              112.0                         __________________________________________________________________________

The results in Tables XI, XII, and XIII clearly show that the catalyticcomposition which contains an impregnated hydrogenation metal, CatalystD, outperforms the catalyst that does not contain any of the impregnatednickel, i.e., Catalyst C.

EXAMPLE VI

Another embodiment of the AMS-1B crystalline borosilicate of the presentinvention was prepared. This borosilicate was prepared by using thefollowing quantities of chemicals: 11,900.0 gm of distilled water; 275.0gm of NaOH; 430.0 gm of H₃ BO₃ ; 1,755.0 gm of tetrapropylammoniumbromide; and 1,623.0 gm of Ludox HS-40. Two batches of this materialwere prepared. Each batch was made from the above quantities ofingredients. The first batch had a pH of 10.61, while the second batchhad a pH of 10.76.

In the case of each batch, five identical portions, each of which wouldfit into a 1-gallon Waring Blendor, were prepared. Then the fiveportions were added to a 5-gallon stirred autoclave for a 7-daycrystallization at a temperature of 329° F. (165° C.). Stirring in theautoclave was maintained at a rate of 250 rpm. Each batch of thecrystallized material was washed from the crystallizer, filtered fromthe crystallization solution, and washed with 5 liters of distilledwater. The resultant borosilicates were then dried and program calcinedat 1,000° F. (538° C.) as described in Example III. The crystallinematerial, in each case, was identified by X-ray diffraction patterns asbeing AMS-1B crystalline borosilicate molecular sieves.

A 200-gm portion of each sieve was cation-exchanged to the hydrogen formof the borosilicate by employing ammonium acetate cation exchange. Each200-gm sample was split into two 100-gm samples for ease ofcation-exchanging. Each 100-gm quantity of crystalline borosilicate wasslurry-exchanged with 200 gm of ammonium acetate that had been dissolvedin 1,500 ml of distilled water at a temperature of 203° F. (95° C.) fora period of 2 hours. The crystalline material was filtered from theexchange solution, washed with approximately 200 ml of distilled water,and filter dried for 2 hours. The dried filter cake was again exchangedaccording to the above-described exchange technique. After the secondexchange, the crystalline material was washed with approximately 4liters of distilled water and filter dried. This air-dried solid wasthen program calcined at a temperature of 1,000° F. (538° C.) for 12hours. The two 100-gm samples from each batch of crystallineborosilicate were blended and the blended material constituted ahydrogen-form of AMS-1B crystalline borosilicate. The blend of the firsttwo 100-gm samples is identified hereinafter as Borosilicate No. 4,while the blend of the second two 100-gm samples is identifiedhereinafter as Borosilicate No. 5.

EXAMPLE VII

In this example, 15 gm of Borosilicate No. 4 were dispersed in 167 gm ofPHF-alumina hydrosol (8.7% solids) which had been obtained from theAmerican Cyanamid Company. The mixture was thoroughly blended in aWaring Blendor. Twelve milliliters of a 1:1 solution of concentratedammonium hydroxide and distilled water were rapidly added to the blendedslurry while the blender was being operated at a high speed for twominutes. The resulting gelled solid was transferred to a forced draftdrying oven to dry for 16 hours at a temperature of 329° F. (165° C.).The dried solid was then program calcined at a temperature of 1,000° F.(538° C.) to provide a catalyst which was made up of 50 wt.%Borosilicate No. 4 and 50 wt.% gamma-alumina. This catalyst isidentified hereinafter as Catalyst E.

EXAMPLE VIII

A catalyst, identified hereinafter as Catalyst F, was prepared withBorosilicate No. 5. The preparation was identical to that of Catalyst Edescribed hereinabove in Example VII.

EXAMPLE IX

A number of additional catalytic compositions were prepared, whichcatalytic compositions employed as starting materials eitherBorosilicate No. 4 or Borosilicate No. 5. Each of these catalysts wasprepared according to the following procedure.

In the case of metal-cation-exchanged samples, the hydrogen-form of thecrystalline borosilicate was exchanged with the appropriate metal saltat a temperature of 194° F. (90° C.) for a period of about 90 to about120 minutes, filtered, washed, dried, and program calcined at atemperature of 1,000° F. (538° C.). The metal-exchanged borosilicate wasmixed with PHF-alumina hydrosol (9 wt.% solids) obtained from theAmerican Cyanamid Company in a Waring Blendor and gelled with aqueousammonia. The resulting gel was dried and calcined at a temperature of1,000° F. (538° C.) for a period of 12 hours. In each case, theresulting catalyst, which contained 50 wt.% crystalline borosilicate and50 wt.% gamma-alumina, was then ground to a 18-to-40-mesh material,i.e., a material that would pass through an 18-mesh screen (U.S. SieveSeries) but would be retained upon a 40-mesh screen (U.S. Sieve Series).

In the case of the impregnated samples, the hydrogen form of theborosilicate was incorporated into a catalyst as described in theparagraph hereinabove. The 18-to-40-mesh particles were then impregnatedusing 1 ml of an aqueous solution of the appropriate metal salt per gramof catalyst. The resulting samples were then dried and calcined at1,000° F. (538° C.) for a period of 12 hours. The drying was conductedin a forced draft oven for a period of 16 hours at a temperature of 329°F. (165° C.).

Table XIV lists various catalysts that were prepared according to thedescriptions provided hereinabove and in Examples VII and VIII. Theparticular metal salt that was employed in the cation-exchanging or theimpregnation and the technique of incorporation are listed for eachcatalyst.

                                      TABLE XIV                                   __________________________________________________________________________    Example     IX     X      XI    XII   XIII  XIV   XV    XVI                   Catalyst    E      F      G     H     I     J     K     L                     __________________________________________________________________________    Metal Source                                                                              --     --     --    Calcium                                                                             H.sub.3 BO.sub.3                                                                    Zn(NO.sub.3).sub.2                                                                  Cr(OAc).sub.3                                                                       Cr(OAc).sub.3                                         Acetate                                       Metal Impregnated                                                                         --     --     --    --    B     --    Cr    Cr                    Metal Exchanged                                                                           --     --     Na    Ca    --    Zn    --    --                    Amount of Metal, %        0.59  0.23  1.5   0.15  0.34  1.7                   Test No.    5      6      7     8     9     10    11    12                    Conditions:                                                                   Temp., °F.                                                                         750    750    750   750   750   750   750   750                       °C.                                                                            399    399    399   399   399   399   399   399                   Press., psig                                                                              200    200    200   200   200   200   200   200                       KPa     1,480  1,480  1,480 1,480 1,480 1,480 1,480 1,480                 Contact Time, sec                                                                         5.2    5.0    5.7   4.5   4.9   4.4   4.9   4.9                   Time on Oil, hrs                                                                          30     6      5     6     106   5     24    45.5                  Hydrogen/HC 5.6    6.6    7.5   7.1   6.0   7.1   6.6   4.5                   Data/Pass                                                                     p-Xylene PATE                                                                             99+    99+    99+   99+   99+   99+   99+   99+                   % Ethylbenzene Loss                                                                       23.3   25.3   12.2  16.8  15.8  19.9  20.7  21.3                  % Xylene Loss                                                                             2.8    3.6    0.8   2.4   1.9   1.5   1.0   0.5                   Ethylbenzene/Xylene                                                                       8.4    7.0    15.0  7.0   8.3   13.0  20.7  42.6                  Loss                                                                          Products                                                                      Paraffins and                                                                             0.01   0.02   0.00  0.00  0.00  0.14  0.18  0.02                  Naphthenes                                                                    Benzene     2.22   2.89   1.17  2.05  1.96  2.29  2.83  2.45                  Toluene     0.38   0.47   0.26  0.51  0.45  0.59  0.53  0.32                  C.sub.9 +   3.29   3.46   1.65  2.6   2.3   2.3   1.22  1.89                  __________________________________________________________________________    Example      XVII    XVIII  XIX   XX     XXI    XXII   XXIII                  Catalyst     L*      M*     N*    N      O      P      Q                      __________________________________________________________________________    Metal Source Cr(OAc).sub.3                                                                         (NH.sub.4).sub.6--                                                                   (NH.sub.4).sub.6--                                                                  (NH.sub.4).sub.6--                                                                   Fe(NO.sub.3).sub.3                                                                   RuCl.sub.3                                                                           Co(NO.sub.3).sub.2                                                            2                                           Mo.sub.7 O.sub.24                                                                    Mo.sub.7 O.sub.24                                                                   Mo.sub.7 O.sub.24                           Metal Impregnated                                                                          Cr      Mo     Mo    Mo     Fe     Ru     --                     Metal Exchanged                                                                            --      --     --    --     --     --     Co                     Amount of Metal, %                                                                         1.7     3.3    5     5      3.5    0.5    0.06                   Test No.     13      14     15    16     17     18     19                     Conditions:                                                                   Temp., °F.                                                                          750     750    750   750    750    750    750                        °C.                                                                             399     399    399   399    399    399    399                    Press., psig 200     200    200   200    200    200    200                        KPa      1,480   1,480  1,480 1,480  1,480  1,480  1,480                  Contact Time, sec                                                                          4.8     5.0    5.3   5.2    4.1    4.3    5.1                    Time on Oil, hrs                                                                           92      98     113   24     21     24     30                     Hydrogen/HC  4.9     5.4    5.5   5.3    5.2    7.0    6.1                    Data/Pass                                                                     p-Xylene PATE                                                                              99+     99+    99+   99+    99+    99+    99+                    % Ethylbenzene Loss                                                                        16.9    23.2   28.7  22.9   14.8   26.7   17.6                   % Xylene Loss                                                                              0.7     0.4    0.4   0.9    1.0    0.4    1.4                    Ethylbenzene/Xylene                                                                        24.1    56     72    25     14.8   63     12.3                   Loss                                                                          Products                                                                      Paraffins and                                                                              0.04    0.09   0.08  0.27   0.01   0.06   0.01                   Naphthenes                                                                    Benzene      2.15    3.3    3.9   3.25   1.52   3.30   1.81                   Toluene      0.28    0.39   0.55  0.59   0.24   0.35   0.33                   C.sub.9 +    1.43    1.07   1.31  1.09   2.10   1.37   2.79                   __________________________________________________________________________    Example      XXIV    XXV    XXVI  XXVII  XXVIII XXIX   XXX                    Catalyst     R       R*     S     T*     U*     V*     W*                     __________________________________________________________________________    Metal Source Co(NO.sub.3).sub.2                                                                    Co(NO.sub.3).sub.2                                                                   Ni(NO.sub.3).sub.2                                                                  Ni(OAc).sub.2                                                                        Ni(NO.sub.3).sub.2 /                                                                 Ni(NO.sub.3).sub.2                                                                   Ni(NO.sub.                                                                    3).sub.2                                                        NH.sub.4 OH                          Metal Impregnated                                                                          Co      Co     --    --     --     Ni     Ni                     Metal Exchanged                                                                            --      --     Ni    Ni     Ni     --     --                     Amount of Metal, %                                                                         1.5     1.5    0.05  1.13   0.71   1.2    1                      Test No.     20      21     22    23     24     25     26                     Conditions:                                                                   Temp., °F.                                                                          750     750    750   750    750    750    750                        °C.                                                                             399     399    399   399    399    399    399                    Press., psig 200     200    200   200    200    200    200                        KPa      1,480   1,480  1,480 1,480  1,480  1,480  1,480                  Contact Time, sec                                                                          5.0     4.9    5.3   5.5    4.3    5.0    5.2                    Time on Oil, hrs                                                                           48      96     30    101    92     101    99                     Hydrogen/HC  5.4     5.4    5.7   6.5    7.2    6.6    5.7                    Data/Pass                                                                     p-Xylene PATE                                                                              99+     99+    99+   99+    99+    99+    99+                    % Ethylbenzene Loss                                                                        26.6    29.6   20.3  17.6   10.6   29.1   30.5                   % Xylene Loss                                                                              1.4     2.5    1.6   1.5    1.1    1.6    1.45                   Ethylbenzene/Xylene                                                                        19      11.8   13.0  11.6   9.6    17.9   21.1                   Loss                                                                          Products                                                                      Paraffins and                                                                              0.03    0.04   0.01  0.09   0.01   0.07   0.12                   Naphthenes                                                                    Benzene      3.40    3.40   2.00  2.30   1.26   3.60   4.01                   Toluene      0.70    0.55   0.37  0.60   0.35   0.70   0.69                   C.sub.9 +    2.03    3.6    2.9   1.71   1.56   2.66   2.33                   __________________________________________________________________________    Example      XXXI    XXXII  XXXIII                                                                              XXXIV  XXXV   XXXVI  XXXVII                 Catalyst     X       Y      Z*    AA*    BB     CC     DD                     __________________________________________________________________________    Metal Source RhCl.sub.3                                                                            RhCl.sub.3                                                                           RhCl.sub.3                                                                          RhCl.sub.3                                                                           PdCl.sub.2                                                                           Pd(NO.sub.3).sub.2                                                                   Pd(NO.sub.3).sub.2     Metal Impregnated                                                                          --      --     Rh    Rh     --     Pd     Pd                     Metal Exchanged                                                                            Rh      Rh     --    --     Pd     --     --                     Amount of Metal, %                                                                         --      --     0.5   0.5    --     0.5    0.5                    Test No.     27      28     29    30     31     32     33                     Conditions:                                                                   Temp., °F.                                                                          750     785    750   800    800    750    800                        °C.                                                                             399     419    399   427    427    399    427                    Press., psig 200     200    200   200    200    200    200                        KPa      1,480   1,480  1,480 1,480  1,480  1,480  1,480                  Contact Time, sec                                                                          6.0     4.0    5.1   3.3    3.2    4.8    2.8                    Time on Oil, hrs                                                                           6       29     101   96     28     29     28                     Hydrogen/HC  6.1     8.1    5.8   6.1    7.2    6.4    6.3                    Data/Pass                                                                     p-Xylene PATE                                                                              99+     99+    99+   99+    99+    99+    99+                    % Ethylbenzene Loss                                                                        18.3    28.2   29.5  33.6   31.7   29.8   35.1                   % Xylene Loss                                                                              0.9     0.9    3.1   0.6    0.7    2.0    0.04                   Ethylbenzene/Xylene                                                                        19.7    30.5   9.4   55     45.3   14.6   885                    Loss                                                                          Products                                                                      Paraffins and                                                                              0.02    0.02   3.81  1.06   0.14   2.5    0.50                   Naphthenes                                                                    Benzene      2.52    3.45   3.14  4.38   4.43   3.4    4.89                   Toluene      0.37    0.69   0.39  0.60   0.60   0.4    0.56                   C.sub.9 +    1.75    2.39   0.87  0.84   1.32   1.01   0.77                   __________________________________________________________________________    Example     XXXVIII                                                                              XXXIX  XL    XLI   XLII  XLIII XLIV  XLV                   Catalyst    EE     FF     GG    HH    II*   JJ*   KK*   LL*                   __________________________________________________________________________    Metal Source                                                                              Pt(NH.sub.3).sub.4 Cl.sub.2                                                          H.sub.2 PtCl.sub.6                                                                   H.sub.2 PtCl.sub.6 /                                                                H.sub.2 PtCl.sub.6 /                                                                Mo--W --    --    --                                              NH.sub.4 OH                                                                         NH.sub.4 OH                                                             WASH  WASH                                          Metal Impregnated                                                                         --     Pt     Pt    Pt    --    Mo--Co                                                                              Mo--Ni                                                                              Ni--Cr                Metal Exchanged                                                                           Pt     --     --    --    --    --    --    --                    Amount of Metal, %                                                                        2.09   0.5    0.5   0.5   3.5 Mo-                                                                             3.5 Mo-                                                                             3.5 Mo-                                                                             1 Ni-                                                       2.5 W 1.5 W 1 Ni  1.7 Cr                Test No.    34     35     36    37    38    39    40    41                    Conditions:                                                                   Temp., °F.                                                                         800    800    750   800   750   750   750   750                       °C.                                                                            427    427    399   427   399   399   399   399                   Press., psig                                                                              200    200    200   200   200   200   200   200                       KPa     1,480  1,480  1,480 1,480 1,480 1,480 1,480 1,480                 Contact Time, sec                                                                         3.7    3.4    5.1   2.6   4.8   4.9   4.8   4.6                   Time on Oil, hrs                                                                          24     22     5.5   20.5  96    121   118   92.5                  Hydrogen/HC 8.3    8.0    6.2   10.0  4.7   6.0   5.1   5.6                   Data/Pass                                                                     p-Xylene PATE                                                                             99+    99+    99+   99+   99+   99+   99+   99+                   % Ethylbenzene Loss                                                                       37.1   43.7   59.4  46.5  24.9  24.9  24.3  15.9                  % Xylene Loss                                                                             -0.23  0.9    6.3   0.2   0.5   0.5   1.2   0.4                   Ethylbenzene/Xylene                                                                       -157   50     9.4   220   49.8  49.8  20.3  39.7                  Loss                                                                          Products                                                                      Paraffins and                                                                             1.90   5.52   12.1  4.43  0.06  0.08  0.17  0.29                  Naphthenes                                                                    Benzene     3.98   3.35   2.94  3.80  3.38  3.34  3.39  2.17                  Toluene     0.60   0.59   0.46  0.61  0.48  0.54  0.62  0.27                  C.sub.9 +   1.21   1.60   0.79  1.01  1.36  1.38  1.42  0.83                  __________________________________________________________________________     *Sulfided.                                                               

In each of the Examples IX through XLV, the percent approach toequilibrium (PATE) for p-xylene is approximately equal to 99+. However,generally, the selectivity of a particular catalyst, i.e., theethylbenzene loss/xylene loss, is large for those catalysts which had acatalytically active metal impregnated thereon. The most preferredcatalyst was the catalyt into which molybdenum was impregnated, i.e.,Catalyst M and Catalyst N, particularly when the catalyst had beenpre-sulfided. Other suitable catalysts were Catalyst P, aruthenium-impregnated catalyst, and Catalyst II, Catalyst JJ, andCatalyst LL, each of which had been impregnated with two metals.

What is claimed is:
 1. A catalytic composition which comprises acrystalline borosilicate and a porous refractory inorganic oxide, saidborosilicate and said inorganic oxide having been intimately admixedwith one another, said borosilicate comprising a molecular sievematerial providing an X-ray diffraction pattern comprising the followingX-ray diffraction lines and assigned strengths:

    ______________________________________                                        d(A)            Assigned Strength                                             ______________________________________                                        11.2 ± 0.2   W- VS                                                         10.0 ± 0.2   W- MS                                                         5.97 ± 0.07  W- M                                                          3.82 ± 0.05  VS                                                            3.70 ± 0.05  MS                                                            3.62 ± 0.05  M- MS                                                         2.97 ± 0.02  W- M                                                          1.99 ± 0.02  VW- M                                                         ______________________________________                                    

and having the following composition in terms of mole ratios of oxides:

    0.9±0.2M.sub.2/n O:B.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O,

wherein M is at least one cation having a valence of n, Y is between 4and about 600, and Z is between 0 and about
 160. 2. The catalyticcomposition of claim 1, wherein said borosilicate and said inorganicoxide have been intimately admixed with one another after saidborosilicate has been calcined.
 3. The catalytic composition of claim 1,wherein said inorganic oxide is an alumina.
 4. The catalytic compositionof claim 1, wherein at least one catalytically-active metal comprisingtungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium,manganese, platinum, palladium, a rare earth metal, or mixtures thereofhas been placed onto said catalytic composition.
 5. The catalyticcomposition of claim 1, wherein at least one catalytically-active metalcomprising tungsten, vanadium, molybdenum, rhenium, nickel, cobalt,chromium, manganese, platinum, palladium, a rare earth metal, ormixtures thereof has been placed onto said borosilicate before saidborosilicate is mixed with said inorganic oxide.
 6. The catalyticcomposition of claim 2, wherein at least one catalytically-active metalcomprising tungsten, vanadium, molybdenum, rhenium, nickel, cobalt,chromium, manganese, platinum, palladium, a rare earth metal, ormixtures thereof is placed onto said calcined borosilicate before saidborosilicate is mixed with said inorganic oxide.
 7. The catalyticcomposition of claim 2, wherein said inorganic oxide is an alumina. 8.The catalytic composition of claim 4, wherein at least onecatalytically-active metal comprising tungsten, vanadium, molybdenum,rhenium, nickel, cobalt, chromium, manganese, platinum, palladium, arare earth metal, or mixtures thereof has been placed onto saidcatalytic composition.
 9. The catalytic composition of claim 4, whereinsaid catalytically-active metal is placed onto said catalyticcomposition by impregnation techniques.
 10. The catalytic composition ofclaim 4, wherein said catalytically-active metal is placed onto theborosilicate of said catalytic composition by ion-exchange.
 11. Thecatalytic composition of claim 6, wherein said catalytically-activemetal is placed onto said borosilicate by ion-exchange.
 12. Thecatalytic composition of claim 6, wherein said catalytically-activemetal is placed onto said borosilicate by impregnation techniques. 13.The catalytic composition of claim 11, wherein said catalytically-activemetal is placed onto said catalytic composition by impregnationtechniques.
 14. The catalytic composition of claim 11, wherein saidcatalytically-active metal is place onto the borosilicate of saidcatalytic composition by ion-exchange.
 15. The catalytic composition ofclaim 9, wherein said catalytically-active metal is molybdenum ornickel.
 16. The catalytic composition of claim 10, wherein saidcatalytically-active metal is nickel.
 17. The catalytic composition ofclaim 6, wherein said inorganic oxide is an alumina.
 18. The catalyticcomposition of claim 11, wherein said catalytically-active metal isnickel.
 19. The catalytic composition of claim 12, wherein saidcatalytically-active metal is molybdenum.
 20. The catalytic compositionof claim 13, wherein said catalytically-active metal is molybdenum ornickel.
 21. The catalytic composition of claim 14, wherein saidcatalytically-active metal is nickel.
 22. The catalytic composition ofclaim 18, wherein said inorganic oxide is an alumina.
 23. The catalyticcomposition of claim 19, wherein said inorganic oxide is an alumina. 24.A catalytic composition that is suitable for the conversion ofhydrocarbon streams, which composition comprises at least onecatalytically-active metal comprising tungsten, vanadium, molybdenium,rhenium, nickel, cobalt, chromium, manganese, platinum, palladium, arare earth metal, or mixtures thereof and a catalytic support comprisinga crystalline borosilicate suspended in and distributed throughout amatrix of a refractory inorganic oxide, which composition has beenprepared by the method which comprises: (1) admixing said borosilicatein a finely-divided state with a hydrosol, sol, or hydrogel of saidinorganic oxide in order to uniformly disperse said borosilicate in saidhydrosol, sol, or hydrogel of said inorganic oxide to form an admixture,said borosilicate comprising a molecular sieve material providing anX-ray diffraction pattern comprising the following X-ray diffractionlines and assigned strengths:

    ______________________________________                                        d(A)            Assigned Strength                                             ______________________________________                                        11.2 ± 0.2   W- VS                                                         10.0 ± 0.2   W- MS                                                         5.97 ± 0.07  W- M                                                          3.82 ± 0.05  VS                                                            3.70 ± 0.05  MS                                                            3.62 ± 0.05  M- MS                                                         2.97 ± 0.02  W- M                                                          1.99 ± 0.02  VW- M                                                         ______________________________________                                    

and having the following composition in terms of mole ratios of oxides:

    0.9±0.2M.sub.2/n O:B.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O,

wherein M is at least one cation, n is the valence of the cation, Y is avalue within the range of 4 to about 600, and Z is a value within therange of 0 to about 160; (2) while continually stirring the admixture,adding a gelling medium to promote gellation and to form a gel; (3)drying said gel at a temperature of about 77° F. (25° C.) to about 392°F. (200° C.) for a period of about 10 minutes to about 100 hours in thepresence of air to form a dried mixture; (4) calcining said driedmixture by heating said dried mixture in air at a maximum rate of 200°F. per hour (111° C. per hour) to a calcination temperature within therange of about 752° F. (400° C.) to about 1,112° F. (600° C.) andmaintaining said dried material at said calcination temperature for aperiod of about 30 minutes to about 20 hours to provide a calcinedcatalytic support material; (5) impregnating said calcined catalyticsupport material with a solution of a heat-decomposable compound of saidcatalytically-active metal to provide an impregnated material; (6)drying said impregnated material at a temperature of about 77° F. (25°C.) to about 392° F. (200° C.) for a period of about 10 minutes to about100 hours in air to obtain a dried impregnated material; and (7)calcining said dried impregnated material by heating said driedimpregnated material in air at a maximum rate of 200° F. per hour (111°C. per hour) to a calcination temperature within the range of about 752°F. (400° C.) to about 1,112° F. (600° C.) and maintaining said driedimpregnated material at said calcination temperature for a period ofabout 30 minutes to about 20 hours to provide said catalyticcomposition.
 25. The catalytic composition of claim 24, wherein saidborosilicate is a borosilicate that has been exchanged at the cationicsites with at least one of the materials selected from the groupconsisting of hydrogen, a rare earth metal, aluminum, a metal of GroupIB, a metal of Group IIB, a metal of Group VIB, a metal of Group VIII,manganese, vanadium, rhenium, and mixtures thereof.
 26. The catalyticcomposition of claim 24, wherein said inorganic oxide is an alumina. 27.The catalytic composition of claim 24, wherein said catalytically-activemetal is a metal of Group VIB of the Periodic Table of Elements or ametal of Group VIII of the Periodic Table of Elements.
 28. The catalyticcomposition of claim 25, wherein said inorganic oxide is an alumina. 29.The catalytic composition of claim 25, wherein said catalytically-activemetal is a metal of Group VIB of the Periodic Table of Elements or ametal of Group VIII of the Periodic Table of Elements.
 30. The catayticcomposition of claim 28, wherein said catalytically-active metal is ametal of Group VIB of the Periodic Table of Elements or a metal of GroupVIII of the Periodic Table of Elements.
 31. The catalytic composition ofclaim 30, wherein said catalytically-active metal is molybdenum whensaid catalytically-active metal is a metal of Group VIB and wherein saidcatalytically-active metal is nickel when said catalytically-activemetal is a metal of Group VIII.
 32. A method for the preparation of acatalytic composition that is suitable for the conversion of hydrocarbonstreams, which method comprises: (1) admixing a crystalline borosilicatein a finely-divided state with a refractory inorganic oxide to form acatalytic support material, said catalytic support material having saidborosilicate suspended in and distributed throughout a matrix of saidinorganic oxide, said borosilicate comprising a molecular sieve materialproviding an X-ray diffraction pattern comprising the following X-raydiffraction lines and assigned strengths:

    ______________________________________                                        d(A)            Assigned Strength                                             ______________________________________                                        11.2 ± 0.2   W- VS                                                         10.0 ± 0.2   W- MS                                                         5.97 ± 0.07  W- M                                                          3.82 ± 0.05  VS                                                            3.70 ± 0.05  MS                                                            3.62 ± 0.05  M- MS                                                         2.97 ± 0.02  W- M                                                          1.99 ± 0.02  VW- M                                                         ______________________________________                                    

and having the following composition in terms of mole ratios of oxides:

    0.9±0.2M.sub.2/n O:B.sub.2 O.sub.3 :YSiO.sub.2 :ZH.sub.2 O,

wherein M is at least one cation, n is the valence of the cation, Y is avalue within the range of 4 to about 600, and Z is a value within therange of 0 to about 160; (2) impregnating said catalytic supportmaterial with a solution of a heat-decomposable compound of acatalytically-active metal to provide an impregnated material; (3)drying said impregnated material at a temperature of about 77° F. (25°C.) to about 392° F. (200° C.) for a period of about 10 minutes to about100 hours in air to obtain a dried impregnated material; and (4)calcining said dried impregnated material at a temperature within therange of about 752° F. (400° C.) to about 1,112° F. (600° C.) for aperiod of about 30 minutes to about 20 hours to provide said catalyticcomposition.
 33. The method of preparation of claim 32, wherein saidinorganic oxide is an alumina and said catalytic support material isprepared by: (1) admixing said borosilicate in a finely-divided statewith said alumina by mulling spray-dried alumina with 5 to 20 wt.%gamma-alumina hydrosol or beta-alumina trihydrate and with saidborosilicate to form a mixture that is suitable for extruding; (2)adding water in an amount that will yield an extrudate having about 20wt.% to about 50 wt.% water; (3) adding, if needed, an extrusion aid anda pore-diameter modifier; (4) extruding said resulting admixture to forman extruded admixture; (5) drying said extruded admixture in air at atemperature of about 77° F. (25° C.) to about 392° F. (200° C.) for aperiod of about 10 minutes to about 20 hours to obtain a driedextrudate; and (6) calcining said dried extrudate at a temperaturewithin the range of about 752° F. (400° C.) to about 1,112° F. (600° C.)for a period of about 30 minutes to about 20 hours to provide a calcinedcataytic support material.
 34. The method of preparation of claim 32,wherein said catalytic support material is prepared by: (1) admixingsaid borosilicate in a finely-divided state with a hydrosol, sol, orhydrogel of said inorganic oxide in order to uniformly disperse saidborosilicate in said hydrosol, sol, or hydrogel of said inorganic oxideto form an admixture; (2) while continually stirring the admixture,adding a gelling medium to promote gellation and to form a gel; (3)drying said gel at a temperature within the range of about 77° F. (25°C.) to about 392° F. (200° C.) for a period of about 10 minutes to about100 hours in air to form a dried mixture; and (4) calcining said driedmixture at a temperature within the range of about 752° F. (400° C.) toabout 1,112° F. (600° C.) for a period of about 20 minutes to about 20hours to provide a calcined catalytic support material.
 35. The methodof claim 32, wherein said borosilicate has been cation-exchanged with asuitable cation selected from the group consisting of hydrogen, a rareearth metal, aluminum, a metal of Group IB, a metal of Group IIB, ametal of Group VIB, a metal of Group VIII, manganese, vandium, rhenium,and mixtures thereof.
 36. The method of claim 32, wherein saidcatalytically-active metal is a metal of Group VIB of the Periodic Tableof Elements or a metal of Group VIII of the Periodic Table of Elements.37. The method of claim 33, wherein said borosilicate has beencation-exchanged with a suitable cation selected from the groupconsisting of hydrogen, a rare earth metal, aluminum, a metal of GroupIB, a metal of Group IIB, a metal of Group VIB, a metal of Group VIII,manganese, vanadium, rhenium, and mixtures thereof.
 38. The method ofclaim 33, wherein said catalytically-active metal is a metal of GroupVIB of the Periodic Table of Elements or a metal of Group VIII of thePeriodic Table of Elements.
 39. The method of claim 34, wherein sidborosilicate has been cation-exchanged with a suitable cation selectedfrom the group consisting of hydrogen, a rare earth metal, aluminum, ametal of Group IB, a metal of Group IIB, a metal of Group VIB, a metalof Group VIII, manganese, vanadium, rhenium, and mixtures thereof. 40.The method of claim 34, wherein said catalytically-active metal is ametal of Group VIB of the Periodic Table of Elements or a metal of GroupVIII of the Periodic Table of Elements.
 41. The method of claim 35,wherein said catalytically-active metal is a metal of Group VIB of thePeriodic Table of Elements or a metal of Group VIII of the PeriodicTable of Elements.
 42. The method of claim 37, wherein saidcataytically-active metal is a metal of Group VIB of the Periodic Tableof Elements or a metal of Group VIII of the Periodic Table of Elements.43. The method of claim 38, wherein, if a metal of Group VIB is employedas the catalytically-active metal, molybdenum is that metal of Group VIBand, if a metal of Group VIII is employed as the cataytically-activemetal, nickel is that metal of Group VIII.
 44. The method of claim 39,wherein said catalytically-active metal is a metal of Group VIB of thePeriodic Table of Elements or a metal of Group VIII of the PeriodicTable of Elements.
 45. The method of claim 42, wherein, if a metal ofGroup VIB is employed as the catalytically-active metal, molybdenum isthat metal of Group VIB and, if a metal of Group VIII is employed as thecatalytically-active metal, nickel is that metal of Group VIII.
 46. Themethod of claim 44, wherein, if a metal of Group VIB is employed as thecatalytically-active metal, molybdenum is that metal of Group VIB and,if a metal of Group VIII is employed as the catalytically-active metal,nickel is that metal of Group VIII.